WO2002092500A1 - Catalytically active separating membrane for producing high-purity hydrogen - Google Patents
Catalytically active separating membrane for producing high-purity hydrogen Download PDFInfo
- Publication number
- WO2002092500A1 WO2002092500A1 PCT/EP2002/004910 EP0204910W WO02092500A1 WO 2002092500 A1 WO2002092500 A1 WO 2002092500A1 EP 0204910 W EP0204910 W EP 0204910W WO 02092500 A1 WO02092500 A1 WO 02092500A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- membrane
- composite membrane
- composite
- metallic layer
- hydrogen
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 150
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000001257 hydrogen Substances 0.000 title claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 claims abstract description 85
- 239000000446 fuel Substances 0.000 claims abstract description 27
- 238000002407 reforming Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 150000002736 metal compounds Chemical class 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 238000005452 bending Methods 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 229910001252 Pd alloy Inorganic materials 0.000 claims 1
- 239000003245 coal Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001960 metal nitrate Inorganic materials 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- WAXDNUVIPREAOK-UHFFFAOYSA-N aluminum methylsilicon(3+) oxosilicon(2+) oxygen(2-) Chemical compound C[Si+3].[Si+2]=O.[O-2].[Al+3].[O-2].[O-2].[O-2] WAXDNUVIPREAOK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0046—Inorganic membrane manufacture by slurry techniques, e.g. die or slip-casting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
- B01D71/0223—Group 8, 9 or 10 metals
- B01D71/02232—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/10—Supported membranes; Membrane supports
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- B01D71/0213—Silicon
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- B01D71/02—Inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/0221—Group 4 or 5 metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/02—Inorganic material
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- B01D71/0223—Group 8, 9 or 10 metals
- B01D71/02231—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B01J35/59—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
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- B01D2325/24—Mechanical properties, e.g. strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00132—Controlling the temperature using electric heating or cooling elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
- C01B2203/041—In-situ membrane purification during hydrogen production
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to the use of a special membrane as a carrier membrane in a composite membrane for a membrane reactor, a special composite membrane and a membrane reactor.
- Membrane reactors are known from the prior art. Membrane reactors are devices with which a reaction and a separation process can be carried out simultaneously on a membrane in the same reaction space. Reformers which generate hydrogen by reforming fuels are also known from the prior art. Such reformers can be used to generate hydrogen for the operation of a fuel cell. It is already known from the prior art to use a membrane reactor as a reformer. For example, Volker Formanski (Hydrogen gas production for supplying fuel gas to low-temperature fuel cells using a membrane reactor for methanol reforming. Schwier.-Ber. VDI, Erasmus 3 (2000), 632 I-III.
- VX pages 84 to 92 in front of a membrane reactor which produces hydrogen by reforming fuels and which consists of a reaction chamber which is filled with a catalytic bulk material, the hydrogen generated under pressure being separated from the reaction chamber by a Pd / Ag membrane.
- the membrane described is a metal tube that is inserted into the reaction chamber.
- the metal tube must have sufficient stability so that it is not damaged or destroyed under the operating conditions in the reaction chamber.
- membrane technology promises an increase in energy efficiency by separating off the product gas and shifting the chemical equilibrium to the hydrogen side
- no practical membranes are known from the prior art for the following reasons that would be suitable for use with fuel cells that use Can operate automobile.
- the membranes described by Formanski are able to separate high-purity hydrogen.
- the membrane must withstand a high pressure differential between the inside and the outside of the reactor. This requirement can only be achieved by using a large layer thickness.
- a membrane with a large layer thickness is sufficiently stable, but only has a low hydrogen permeability, so that the hydrogen produced can penetrate such a membrane only slowly. This is the dilemma that cannot be solved by the prior art.
- the present invention uses a flexible, porous membrane as a carrier membrane in an electrically heatable composite membrane for a membrane reactor in which hydrogen is generated by reforming fuels, the composite membrane comprising the carrier membrane and a metallic layer catalyzing the reforming and for the selective separation of the hydrogen produced from the membrane reactor.
- Another aspect of the present invention is an electrically heatable, composite membrane, comprising a flexible, porous carrier membrane and a metallic layer, characterized in that
- the electrically heatable, flexible, porous membrane is a composite that has an openwork support, preferably a woven and / or nonwoven, and a porous one
- the membrane according to the invention catalyzes the synthesis gas reaction, separates high-purity hydrogen from the reaction mixture and is mechanically sufficiently stable against large pressure differences. Furthermore, the membrane according to the invention can be heated electrically. A membrane according to the invention is therefore particularly suitable for synthesis gas reactors for generating high-purity hydrogen, which is required, for example, for electricity generation in a fuel cell.
- the membrane according to the invention consists of a mechanically stable, ceramic, preferably electrically conductive, carrier membrane. This is equipped with a coating that is both catalytically active and stores hydrogen.
- the present invention offers the advantage that the reaction enthalpy required for the syngas process can be introduced to the catalytically active centers in the reforming process in a controlled manner by heating the membrane.
- this makes it possible to handle possible load change processes and cold start phases without any problems, particularly in mobile use.
- the membranes according to the invention can in particular catalyze the generation of hydrogen from hydrocarbons and can separate hydrogen gas in such a way that highly pure hydrogen is produced as the product.
- Partial oxidation means that the synthesis gas reaction is carried out in the presence of oxygen, with at least some of the hydrocarbons being burned to produce the necessary enthalpy of reaction, so that coking of the fuels occurs.
- the membranes according to the invention offer sufficient mechanical stability in relation to the pressure difference between the interior of the synthesis gas reactor and the exterior.
- the membranes according to the invention are preferably used in membrane reactors for the production of high-purity hydrogen.
- the use of a high-purity hydrogen gas is advantageous for the operation of a fuel cell in mobile and stationary use in two ways.
- the energy efficiency of the fuel cell can be increased considerably.
- the catalyst poisons, such as carbon monoxide and sulfur-containing compounds, which are present in traces in the reforming technologies used to date are missing, so that the service life of the fuel cell can be increased compared to the current status.
- the composite membrane according to the invention can in particular comprise a composite material according to DE 19741498 AI or DE 19640461 AI as the carrier membrane, which is coated with a thin metallic layer consisting of a hydrogen-storing material with sufficiently good adhesion, uniformly strong.
- Suitable materials for the metallic layer are all materials which are capable of reversibly depositing hydrogen in their interior with a proportion of 1% by weight to 30% by weight.
- the metallic layer comprises in particular one or more of the following metals: palladium, silver, gold, copper, cobalt, nickel, ruthenium, rhodium, zinc, aluminum, titanium, indium, vanadium, tungsten, rhenium, tungsten, molybdenum and / or rare earth metals ,
- Palladium is preferred, to which silver or copper is particularly preferably added for the purpose of improving the hydrogen permeability and its mechanical properties while absorbing hydrogen in a concentration range of 15 to 25% by weight, preferably 20% by weight.
- the thickness of the metallic layer is 0.1 ⁇ m to 1000 ⁇ m, preferably less than 5 ⁇ m.
- the selection of the metallic layer for the membrane according to the invention is preferably to be made such that the surface of the metallic layer is catalytically sufficiently active for the synthesis gas reaction.
- highly active catalyst centers can additionally be applied to the surface in order to increase the catalytic activity.
- These highly active catalysts which require the synthesis gas reactions are applied in the form of submicron-sized dots with a size of 20 nm to 1 ⁇ m, preferably 100 nm, regularly with average lateral distances of 0.1 ⁇ m to 50 ⁇ m. The following materials are used:
- the elements platinum, palladium, rhodium, rhenium, nickel, copper and / or cobalt can be used as catalysts for the synthesis gas reaction. These elements can be in metallic form alone or in alloy with other metals or in oxidized or reduced form can be used in catalytically active compounds with other elements.
- the composition of the catalyst centers provided on the surface of the metallic layer is different from the composition of the metallic layer.
- the metallic layer of the flexible composite membrane can have a pattern of alternating concave and convex regions in order to compensate and / or to avoid stresses due to volume changes due to hydrogen absorption.
- the volume changes always occur when hydrogen is sorbed by the selective layer, and this is the case in the separation process. Because the volume change due to hydrogen absorption leads to a change in the surface of the membrane, which can go so far that cracks form in the membrane, and then separation is no longer possible with this membrane. This problem comes to the fore the thinner and more sensitive the hydrogen-selective layers become. This also occurs with tubular membranes, but is not quite as problematic as with plate-shaped systems, since the geometry of the tubular design means that many stresses can be absorbed. This means that changes in the surface only occur after 10 times more cycles with tubular membranes than with plate-shaped membranes. But the problem as such is not negligible.
- the metallic layers which preferably have a pattern of alternating concave and convex regions, can better absorb stresses that arise from changes in volume of the selective layers and thereby show a significantly improved long-term stability. These tensions are guaranteed by the special static of the metallic layer on the carrier membrane, which has a perforated carrier.
- the "corrugated" structure of the surface with "hills” at the uninterrupted areas and “valleys” at the open areas of the openwork support leads to this effect.
- the fact that the entire membrane is a "mountain and Valley structure "at irregular or preferably regular intervals, ie a structure with alternating concave and convex areas, can be degraded better by the volume changes induced by hydrogen sorption.
- the metallic layer must not be too thick, so that these advantages are canceled out by the disadvantage of an excessively thick layer.
- the metallic layer should be less than 5 ⁇ m thick, particularly preferably thinner than 2 ⁇ m and very particularly preferably less than 1 ⁇ m.
- the coefficient of thermal expansion of the carrier membrane and the coefficient of thermal expansion of the metallic layer differ by less than 15%, preferably less than 10%.
- the thermal expansion coefficient of the carrier membrane and the thermal expansion coefficient of the metal layer are very particularly preferably approximately the same size. This is ensured by the suitable choice of the openwork carrier, which is preferably made of metal. In this way, cracks in the metallic layer due to temperature changes can be avoided.
- the surface of the membrane according to the invention is active as a catalyst.
- the synthesis gas reaction takes place on the surface of the hydrogen-storing metallic layer or, in a further embodiment of the invention, also on specially applied, highly active, submicron-scale catalyst dots.
- the membranes according to the invention for producing high-purity hydrogen from the reforming process have the property of depositing hydrogen — usually atomically — into the crystalline structure at interstitial sites at high hydrogen gas partial pressure until chemical equilibrium is reached. When the hydrogen gas partial pressure is reduced, the gas is released again. A high hydrogen gas pressure prevails within the membrane reactor during operation. In contrast, a greatly reduced hydrogen pressure prevails outside the reactor.
- the metallic Layer, consisting of the hydrogen-storing material, thus represents a suitable membrane for the separation of high-purity hydrogen.
- the perforated support of the composite material of the composite membrane according to the invention comprises a metal mesh, preferably a stainless steel mesh and / or stainless steel fleece.
- the metal mesh can be easily contacted electrically, so that an electrical current to be applied creates ohmic heat in the immediate vicinity of the reaction. This heat generated in this way reaches the catalytically active areas of the membrane according to the invention and can provide the endothermic reaction enthalpy required for the synthesis gas reaction.
- This type of energy supply allows targeted heating of the reactive centers, so that losses due to the heating of gases inside the reactor can be largely avoided.
- the electrical heating can be regulated in a very short time.
- the generation of hydrogen can thus be regulated in a finely adjustable manner. This property is of great advantage for the needs of the fuel cell automobile, because it makes it particularly easy to manage load change processes.
- cold start phases can be greatly shortened by rapid electrical heating of the reactive centers.
- the rate of hydrogen formation when using the composite membrane according to the invention in the reforming preferably corresponds essentially to the rate of hydrogen passage through the composite membrane.
- the membrane according to the invention offers sufficient stability due to the perforated support inside, in particular with respect to the high pressure difference between the inside and the outside of the reactor.
- the flexible, openwork support of the composite membrane according to the invention can be a
- a carrier which has been made permeable to matter by treatment with laser beams, ion beams or an etchant can also be used as a flexible, openwork carrier.
- the openwork carrier preferably comprises fibers and / or filaments with a diameter of 1 to 150 ⁇ m, preferably 1 to 20 ⁇ m, and / or threads with a diameter of 5 to 150 ⁇ m, preferably 20 to 70 ⁇ m.
- the openwork carrier is a woven fabric
- this is preferably a woven fabric made of 11-Tex yarns with 5-50 warp or weft threads and in particular 20-28 warp and 28-36 weft threads. 5,5-Tex yarns with 10-50 warp or weft threads are particularly preferred, and 20-28 warp and 28-36 weft threads are preferred.
- the composite membrane according to the invention can preferably be operated at a temperature between 300 ° C. and 900 ° C., particularly preferably at more than 500 ° C., very particularly preferably at more than 800 ° C.
- the fuel which is preferably used when the composite membrane according to the invention is used in a membrane reactor for reforming fuels comprises a hydrocarbon or an alcohol.
- the fuel particularly preferably comprises methane, ethane, propane and / or butane or methanol and / or ethanol.
- the metallic layer can be heated.
- the metallic layer is very particularly preferably indirectly heated by resistance heating.
- the composite membrane according to the invention is preferably used in a membrane reactor which is a reformer for a fuel cell for stationary or mobile applications.
- a composite membrane according to the invention can be operated in a membrane reactor at a pressure of 0.5 to 200 bar (0.5 to 200 ⁇ 10 5 Pa).
- the composite membrane according to the invention is obtainable from
- step (F) optionally repeating steps (A) through (E) with the composite from step (E) using mixtures containing particles of smaller particle size to create a multilayer composite.
- sols such as titanium nitrate sol, zirconium nitrate sol or silica sol or a sol of aluminum oxide can be used as dispersions.
- the dispersions can also be obtained by hydrolysis of a metal compound, semimetal compound or mixed metal compound in a medium, such as water, alcohol or an acid.
- the compound to be hydrolyzed is preferably a metal nitrate, a metal chloride, a metal carbonate, a metal alcoholate compound or a semimetal alcoholate compound, particularly preferably at least one
- the hydrolyzed compound can be peptized with an acid, preferably with a 10 to 60% acid, preferably with a mineral acid selected from sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid and nitric acid or a mixture of these acids.
- an acid preferably with a 10 to 60% acid, preferably with a mineral acid selected from sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid and nitric acid or a mixture of these acids.
- An inorganic component with a grain size of 1 to 10,000 nm can be suspended in the sol.
- At least one inorganic component which comprises at least one compound from the oxides of the subgroup elements or from the elements of the 3rd to 5th main group, preferably oxides, selected from the oxides of the elements Sc, Y, Ti, Zr, Nb, Ce, V , Cr, Mo, W, Mn, Fe, Co, B, AI, In, TI, Si, Ge, Sn, Pb and Bi, such as B. Y 2 O 3 , ZrO 2 , Fe 2 O 3 , Fe 3 O 4 , SiO 2 , Al 2 O 3 , suspended.
- the inorganic component can also be aluminosilicates, aluminum phosphates, zeolites or partially exchanged zeolites, such as, for. B.
- ZSM-5, Na-ZSM-5 or Fe-ZSM-5 or amorphous microporous mixed oxides which can contain up to 20% non-hydrolyzable organic compounds, such as. B. vanadium oxide, silicon oxide glass or aluminum oxide-silicon oxide-methyl silicon sesquioxide glasses.
- the mass fraction of the suspended component is preferably 0.1 to 500 times the hydrolyzed compound used.
- the metal oxide which is mixed with the dispersion in step (C) is preferably selected from the group consisting of titanium oxide, aluminum oxide, silicon oxide and zirconium oxide or from their mixed oxides and the hydrolyzable metal compound is preferably a compound of titanium, zirconium, silicon, or aluminum.
- the suspended compound When using a mesh fabric with a mesh size of z. B. 100 microns as an openwork carrier can preferably be used to increase the freedom from cracks, the suspended compound with a grain size of at least
- the composite material can preferably be a
- Thickness from 5 to 1000 microns, particularly preferably from 50 to 150 microns.
- the mixture of dispersion and compounds to be suspended preferably has a ratio
- the mixture can be solidified by heating the composite of mixture and openwork carrier to 50 to 1000 ° C., preferably about 100 ° C. In a particular embodiment, the composite is exposed to a temperature of 50 to 100 ° C. for 10 minutes to 5 hours. In a further particular embodiment, the composite is exposed to a temperature of 100 to 800 ° C. for 1 second to 10 minutes.
- the composite can be heated with heated air, hot air, infrared radiation, microwave radiation or electrically generated heat.
- the mixture can be solidified by the mixture being applied to a preheated carrier and thus being solidified immediately after the application.
- the perforated carrier is rolled off a roll at a speed of 1 m / h to 1 m / s, on an apparatus which Contacted mixture with the carrier and then to another apparatus that allows the mixture to solidify by heating, and the composite material thus produced is rolled up on a second roll. In this way it is possible to manufacture the composite material continuously.
- a ceramic or inorganic layer is applied to a composite material. This can be done, for example, by laminating a green (unsintered) ceramic layer or an inorganic layer, which is present on an auxiliary film, onto the carrier or by treating the composite material with a further suspension (mixture) as described above. This bond can be solidified by heating.
- the green ceramic layer used preferably contains a nanocrystalline powder of a semimetal or metal oxide, such as. As aluminum oxide, titanium dioxide or zirconium dioxide.
- the green layer can contain an organic binder.
- a composite material is obtained which has a pore gradient.
- supports for the production of composite materials with a specific pore size the pore or mesh size of which is not suitable for producing a composite material with the required pore size.
- This can e.g. B. be the case when a composite material with a pore size of 0.25 microns is to be produced using a carrier with a mesh size of over 300 microns.
- the composite material obtained in this way can now be used as Support membrane with a smaller mesh or pore size can be used.
- a further suspension can be applied to this carrier membrane, which has a compound with a grain size of 0.5 ⁇ m.
- the insensitivity to cracks in composite materials with large mesh or pore widths can also be improved by applying suspensions to the carrier which have at least two suspended compounds.
- Compounds to be suspended are preferably used which have a particle size ratio of 1: 1 to 1:20, particularly preferably 1: 1.5 to 1: 2.5.
- the weight fraction of the grain size fraction with the smaller grain size should not exceed a proportion of at most 50%, preferably 20% and very particularly preferably 10%, of the total weight of the grain size fraction used.
- a hydrogen-permeable adhesion-promoting layer is provided between the perforated support and the metallic layer.
- the composite membrane is preferably elastic and preferably tolerates a bending radius down to 100 m, preferably down to 10 cm, and particularly preferably tolerates a maximum bending radius in the range from 1 to 100 mm without the metallic layer subjected to pressure forming cracks.
- the composite membrane according to the invention is preferably an asymmetrical composite membrane.
- the metallic layer is applied to the carrier membrane by known coating methods, such as CVD (chemical vapor deposition); PVD (physical vapor deposition, in particular sputtering or plasma coating); Electroplating or electroless plating. These processes are suitable for applying hydrogen-selective and catalytically active layers in good quality to the support membranes.
- the catalyst centers (dots) are preferably applied to the metallic layer by spraying on a suspension which contains the catalyst-active component.
- the catalyst centers can, however, also be applied by the same methods as the application of the metallic layer on the support membrane. Before that, however, a grid-like pattern is applied to the metal layer. The catalyst centers are then applied to the metal layer in the spaces between the grid, at the intervals predetermined by the grid. The grid is then preferably removed again. If the grid is permeable to hydrogen and inert to the reforming and the catalytic activity of the catalyst centers is sufficient, the grid can also remain on the metallic layer.
- the present invention also provides a membrane reactor comprising a composite membrane according to the invention.
- the membrane reactor is preferably operated continuously.
Abstract
The invention relates to the use of a flexible, porous membrane as a support membrane in an electrically heatable composite membrane for a membrane reactor wherein hydrogen is produced by reforming fuel. The composite membrane comprises a support membrane and a metallic layer catalysing the reformation and is used to selectively separate the produced hydrogen from the membrane reactor.
Description
Katalytisch aktive Trennmembranen für die Erzeugung von hochreinem WasserstoffCatalytically active separation membranes for the production of high-purity hydrogen
Die vorliegende Erfindung betrifft die Verwendung einer speziellen Membran als Trägermembran in einer Verbundmembran für einen Membranreaktor, eine spezielle Verbundmembran sowie einen Membranreaktor.The present invention relates to the use of a special membrane as a carrier membrane in a composite membrane for a membrane reactor, a special composite membrane and a membrane reactor.
Membranreaktoren sind aus dem Stand der Technik bekannt. Membranreaktoren sind Vorrichtungen mit denen im gleichen Reaktionsraum gleichzeitig eine Reaktion und an einer Membran ein Trennverfahren durchgeführt werden kann. Reformer, die durch Reformierung von Brennstoffen Wasserstoff erzeugen, sind ebenfalls aus dem Stand der Technik bekannt. Solche Reformer können eingesetzt werden, um Wasserstoff für den Betrieb einer Brennstoffzelle zu erzeugen. Aus dem Stand der Technik ist bereits bekannt einen Membranreaktor als Reformer einzusetzen. So schlägt Volker Formanski (Hydrogen gas production for supplying fuel gas to low-temperature fuel cells using a membrane reactor for methanol reforming. Fortschr.-Ber. VDI, Reihe 3 (2000), 632 I-III. V-X, Seiten 84 bis 92) einen Membranreaktor vor, der durch Reformierung von Brennstoffen Wasserstoff erzeugt, und der aus einer Reaktionskammer besteht, die mit einem katalytischen Schüttgut gefüllt wird, wobei der unter Druck erzeugte Wasserstoff durch eine Pd/Ag-Membran aus der Reaktionskammer abgetrennt wird. Bei der beschriebenen Membran handelt es sich um ein Metallröhrchen, das in die Reaktionskammer eingeführt wird. Das Metallröhrchen muss eine ausreichende Stabilität aufweisen, um unter den Betriebsbedingungen in der Reaktionskammer nicht beschädigt oder zerstört zu werden. Zur Verbesserung der Stabilität einer Palladiummembran ist bereits bekannt eine mikroporöse Trägerschicht einzusetzen, auf der eine Ausgleichsschicht und die eigentliche Membranschicht vorgesehen sind. Obwohl die Membrantechnologie eine Erhöhung des energetischen Wirkungsgrads durch die Abtrennung des Produktgases und Verschiebung des chemischen Gleichgewichts auf die Seite des Wasserstoffs verspricht, sind aus dem Stand der Technik aus folgenden Gründen keine praxistauglichen Membranen bekannt, die geeignet wären mit Brennstoffzellen verwendet zu werden, die ein Automobil betreiben können. Die von Formanski beschriebenen Membranen sind zwar in der Lage hochreinen Wasserstoff abzutrennen. Jedoch muss die Membran einem hohen Druckgefälle zwischen dem Inneren and dem Äußeren des Reaktorgeiaßes standhalten.
Diese Anforderung kann nur durch die Verwendung einer großen Schichtdicke erreicht werden. Eine Membran mit einer großen Schichtdicke ist zwar genügend stabil, bietet aber nur eine geringe Wasserstoffdurchlässigkeit, so dass der entstehende Wasserstoff eine derartige Membran nur langsam durchdringen kann. Darin besteht das Dilemma, das vom Stand der Technik nicht gelöst werden kann.Membrane reactors are known from the prior art. Membrane reactors are devices with which a reaction and a separation process can be carried out simultaneously on a membrane in the same reaction space. Reformers which generate hydrogen by reforming fuels are also known from the prior art. Such reformers can be used to generate hydrogen for the operation of a fuel cell. It is already known from the prior art to use a membrane reactor as a reformer. For example, Volker Formanski (Hydrogen gas production for supplying fuel gas to low-temperature fuel cells using a membrane reactor for methanol reforming. Schwier.-Ber. VDI, Reihe 3 (2000), 632 I-III. VX, pages 84 to 92 ) in front of a membrane reactor which produces hydrogen by reforming fuels and which consists of a reaction chamber which is filled with a catalytic bulk material, the hydrogen generated under pressure being separated from the reaction chamber by a Pd / Ag membrane. The membrane described is a metal tube that is inserted into the reaction chamber. The metal tube must have sufficient stability so that it is not damaged or destroyed under the operating conditions in the reaction chamber. To improve the stability of a palladium membrane, it is already known to use a microporous support layer on which a compensating layer and the actual membrane layer are provided. Although membrane technology promises an increase in energy efficiency by separating off the product gas and shifting the chemical equilibrium to the hydrogen side, no practical membranes are known from the prior art for the following reasons that would be suitable for use with fuel cells that use Can operate automobile. The membranes described by Formanski are able to separate high-purity hydrogen. However, the membrane must withstand a high pressure differential between the inside and the outside of the reactor. This requirement can only be achieved by using a large layer thickness. A membrane with a large layer thickness is sufficiently stable, but only has a low hydrogen permeability, so that the hydrogen produced can penetrate such a membrane only slowly. This is the dilemma that cannot be solved by the prior art.
Es ist daher Aufgabe der Erfindung eine Membran für einen Membranreaktor in dem durch Reformierung von Brennstoffen Wasserstoff erzeugt wird, bereitzustellen, wobei die Membran eine hohe Wasserstoffdurchlässigkeit und Selektivität und gleichzeitig eine große Stabilität aufweist und so geeignet ist in einem Membranreaktor eingesetzt zu werden bei dem die Reformierungsreaktion unter hohem Druck und/oder unter wechselnden Druckbedingungen abläuft.It is therefore an object of the invention to provide a membrane for a membrane reactor in which hydrogen is produced by reforming fuels, the membrane having high hydrogen permeability and selectivity and at the same time great stability and is thus suitable for use in a membrane reactor in which the Reforming reaction takes place under high pressure and / or under changing pressure conditions.
Diese Aufgabe wird gemäß der Ansprüche gelöst. Die vorliegende Erfindung verwendet eine flexible, poröse Membran als Trägermembran in einer elektrisch beheizbaren Verbundmembran für einen Membranreaktor, in dem durch Reformierung von Brennstoffen Wasserstoff erzeugt wird, wobei die Verbundmembran die Trägermembran und eine die Reformierung katalysierende metallische Schicht umfasst und zur selektiven Abtrennung des erzeugten Wasserstoffs aus dem Membranreaktor dient.This object is achieved according to the claims. The present invention uses a flexible, porous membrane as a carrier membrane in an electrically heatable composite membrane for a membrane reactor in which hydrogen is generated by reforming fuels, the composite membrane comprising the carrier membrane and a metallic layer catalyzing the reforming and for the selective separation of the hydrogen produced from the membrane reactor.
Ein weiterer Gesichtspunkt der vorliegenden Erfindung ist eine elektrisch beheizbare, Verbundmembran, umfassend eine flexible, poröse Trägermembran und eine metallische Schicht, dadurch gekennzeichnet, dassAnother aspect of the present invention is an electrically heatable, composite membrane, comprising a flexible, porous carrier membrane and a metallic layer, characterized in that
(a) die elektrisch beheizbare flexible, poröse Membran ein Verbundstoff ist, der einen durchbrochenen Träger, vorzugsweise ein Gewebe und/oder Vlies sowie ein poröses(a) the electrically heatable, flexible, porous membrane is a composite that has an openwork support, preferably a woven and / or nonwoven, and a porous one
Keramikmaterial umfasst,Includes ceramic material,
(b) die metallische Schicht geeignet ist(b) the metallic layer is suitable
(bl) eine Reaktion zu katalysieren, bei der Wasserstoff gebildet wird, wenn die Verbundmembran mit einem Gemisch aus Methan und Wasser bei einer Temperatur von 700 °C kontaktiert wird sowie(bl) to catalyze a reaction in which hydrogen is formed when the composite membrane is contacted with a mixture of methane and water at a temperature of 700 ° C. and
(b2) gebildeten Wasserstoff selektiv abzutrennen und andere Bestandteile des
Reaktionsgemisches zurückzuhalten.(b2) selectively separate hydrogen formed and other components of the Withhold reaction mixture.
Die erfindungsgemäße Membran katalysiert die Synthesegasreaktion, trennt hochreinen Wasserstoff aus dem Reaktionsgemisch ab und ist mechanisch genügend stabil gegenüber großen Druckunterschieden. Ferner kann die erfindungsgemäße Membran elektrisch beheizt werden. Daher ist eine erfindungsgemäße Membran besonders für Synthesegasreaktoren zur Erzeugung von hochreinen Wasserstoff geeignet, der beispielsweise für die Verstromung in einer Brennstoffzelle erforderlich ist.The membrane according to the invention catalyzes the synthesis gas reaction, separates high-purity hydrogen from the reaction mixture and is mechanically sufficiently stable against large pressure differences. Furthermore, the membrane according to the invention can be heated electrically. A membrane according to the invention is therefore particularly suitable for synthesis gas reactors for generating high-purity hydrogen, which is required, for example, for electricity generation in a fuel cell.
Die erfindungsgemäße Membran besteht aus einer mechanisch stabilen, keramischen, vorzugsweise elektrisch leitfähigen, Trägermembran. Diese wird mit einer sowohl katalytisch aktiven, als auch Wasserstoff speichernden Beschichtung ausgestattet.The membrane according to the invention consists of a mechanically stable, ceramic, preferably electrically conductive, carrier membrane. This is equipped with a coating that is both catalytically active and stores hydrogen.
Durch den Einsatz der erfindungsgemäßen Membranen in einem Reformer zur Bereitstellung von Wasserstoff für eine Brennstoffzelle kann auf nachgeschaltete Shift-Reaktionsstufen verzichtet werden.The use of the membranes according to the invention in a reformer to provide hydrogen for a fuel cell means that downstream shift reaction stages can be dispensed with.
Die vorliegende Erfindung bietet den Vorteil, dass den im Reformingprozess katalytisch aktiven Zentren die für den Synfhesegasprozess notwendige Reaktionsenthalpie durch Beheizen der Membran geregelt eingebracht werden kann. Vorteilhafterweise sind dadurch insbesondere beim mobilen Einsatz mögliche Lastwechselvorgänge und Kaltstartphasen problemlos zu beherrschen.The present invention offers the advantage that the reaction enthalpy required for the syngas process can be introduced to the catalytically active centers in the reforming process in a controlled manner by heating the membrane. Advantageously, this makes it possible to handle possible load change processes and cold start phases without any problems, particularly in mobile use.
Die erfindungsgemäßen Membranen können in einem Synthesegasreaktor insbesondere die Erzeugung von Wasserstoff aus Kohlenwasserstoffen katalysieren und die Abtrennung von Wasserstoffgas derart bewirken, dass als Produkt hochreiner Wasserstoff entsteht.In a synthesis gas reactor, the membranes according to the invention can in particular catalyze the generation of hydrogen from hydrocarbons and can separate hydrogen gas in such a way that highly pure hydrogen is produced as the product.
Durch eine elektrische Beheizung der erfmdungsgemäßen Membran können im Bereich derBy electrical heating of the membrane according to the invention, in the area of
Reaktionszone sehr hohe Temperaturen erreicht werden. Damit kann die Synthesegasreaktion ohne Sauerstoff ausgeführt werden und einer Verkokung entgegengewirkt werden. Somit kann ein großer Nachteil gemäß dem Stand der Technik vermieden werden, bei dem die für die
Synthesesgasreaktion notwendige Energie durch partielle Oxidation dem Prozess zugeführt wird. Partielle Oxidation heißt, dass die Synthesesgasreaktion in Gegenwart von Sauerstoff durchgeführt wird, wobei zumindest ein Teil der Kohlenwasserstoffe für die Erzeugung der notwendigen Reaktionsenthalpie verbrannt wird, so dass eine Verkokung der Brennstoffe auftritt.Reaction zone very high temperatures can be reached. This enables the synthesis gas reaction to be carried out without oxygen and counteracts coking. Thus, a great disadvantage can be avoided according to the prior art, in which the for the Synthesis gas reaction necessary energy is supplied to the process by partial oxidation. Partial oxidation means that the synthesis gas reaction is carried out in the presence of oxygen, with at least some of the hydrocarbons being burned to produce the necessary enthalpy of reaction, so that coking of the fuels occurs.
Die erfmdungsgemäßen Membranen bieten gegenüber dem Druckunterschied zwischen dem Inneren des Synthesegasreaktors and dem Außenraum genügend mechanische Stabilität.The membranes according to the invention offer sufficient mechanical stability in relation to the pressure difference between the interior of the synthesis gas reactor and the exterior.
Die erfindungsgemäßen Membranen finden bevorzugt Einsatz in Membranreaktoren für die Erzeugung von hochreinem Wasserstoff. Der Einsatz eines hochreinen Wasserstoffgases ist für den Betrieb einer Brennstoffzelle im mobilen and stationären Einsatz in zweierlei Hinsicht vorteilhaft. Einerseits kann der energetische Wirkungsgrad der Brennstoffzelle erheblich gesteigert werden. Andererseits fehlen die bei den bisher eingesetzten Reformertechnologien in Spuren anfallenden Katalysatorgifte, wie zum Beispiel Kohlenmonoxid und schwefelhaltige Verbindungen, so dass die Standzeiten der Brennstoffzelle gegenüber dem jetzigen Stand erhöht werden können.The membranes according to the invention are preferably used in membrane reactors for the production of high-purity hydrogen. The use of a high-purity hydrogen gas is advantageous for the operation of a fuel cell in mobile and stationary use in two ways. On the one hand, the energy efficiency of the fuel cell can be increased considerably. On the other hand, the catalyst poisons, such as carbon monoxide and sulfur-containing compounds, which are present in traces in the reforming technologies used to date are missing, so that the service life of the fuel cell can be increased compared to the current status.
Insbesondere ist es vorteilhaft die Reaktionsenthalpie gezielt and regelbar unmittelbar am Ort der chemischen Umsetzung einzubringen, insbesondere bei den regelbaren Reformerstufen für das Brennstoffzellenautomobil. Sowohl Kaltstartphasen als auch Lastwechselvorgange können somit sicher beherrscht werden. Durch den kompletten Wegfall von Shift-Reaktionstufen und dem hohen erzielbaren energetischen Wirkungsgrad bei Einsatz der erfindungsgemäßen Membran, gelingt eine sehr kompakte Bauweise des Membranreaktors für die Wasserstofferzeugung. Insbesondere bedingt durch die kompakte Bauweise der Synthesegasreaktionstufe für das Brennstoffzellenautomobil treten zwischen Innenraurn des Reaktors and Außenraum erhebliche Druckunterschiede auf, die von der erfindungsgemäßen Membran durch eine hohe mechanische Stabilität sicher beherrscht werden. Dabei wird das Abtrennverhalten durch ein sehr hohes Diffusions vermögen für das Produkt Wasserstoffgas durch die Membran begünstigt.
Die erfindungsgemäße Verbundmembran kann insbesondere einen Verbundwerkstoff gemäß der DE 19741498 AI oder der DE 19640461 AI als Trägermembran umfassen, der mit einer dünnen metallischen Schicht, bestehend aus einem wasserstoffspeichernden Material, mit ausreichend guter Haftung, gleichmäßig stark beschichtet ist.In particular, it is advantageous to introduce the reaction enthalpy in a targeted and controllable manner directly at the site of the chemical conversion, in particular in the controllable reformer stages for the fuel cell automobile. Both cold start phases and load change processes can thus be safely mastered. Due to the complete elimination of shift reaction stages and the high achievable energy efficiency when using the membrane according to the invention, a very compact design of the membrane reactor for hydrogen production is possible. In particular due to the compact design of the synthesis gas reaction stage for the fuel cell automobile, considerable pressure differences occur between the interior of the reactor and the exterior, which are reliably controlled by the membrane according to the invention due to the high mechanical stability. The separation behavior is promoted by a very high diffusion capacity for the product hydrogen gas through the membrane. The composite membrane according to the invention can in particular comprise a composite material according to DE 19741498 AI or DE 19640461 AI as the carrier membrane, which is coated with a thin metallic layer consisting of a hydrogen-storing material with sufficiently good adhesion, uniformly strong.
Als Materialien für die metallische Schicht eignen sich alle Materialien, die in der Lage sind, Wasserstoff mit einem Anteil von 1 Gew. % bis 30 Gew. % in ihrem Inneren reversibel zu deponieren. Die metallische Schicht umfasst dabei insbesondere eines oder mehrere der folgenden Metalle: Palladium, Silber, Gold, Kupfer, Kobalt, Nickel, Ruthenium, Rhodium, Zink, Aluminium, Titan, Indium, Vanadium, Wolfram, Rhenium, Wolfram, Molybdän und/oder Seltenerdmetalle.Suitable materials for the metallic layer are all materials which are capable of reversibly depositing hydrogen in their interior with a proportion of 1% by weight to 30% by weight. The metallic layer comprises in particular one or more of the following metals: palladium, silver, gold, copper, cobalt, nickel, ruthenium, rhodium, zinc, aluminum, titanium, indium, vanadium, tungsten, rhenium, tungsten, molybdenum and / or rare earth metals ,
Bevorzugt ist dabei Palladium, dem besonders bevorzugt zum Zwecke einer Verbesserung der Wasserstoffdurchlässigkeit und seiner mechanischen Eigenschaften unter Wasserstoffaufhahme Silber oder Kupfer in einem Konzentrationsbereich von 15 bis 25 Gew.-%, vorzugsweise 20 Gew. % hinzulegiert wird. Die Dicke der metallischen Schicht beträgt 0,1 μm bis 1000 μm, vorzugsweise weniger als 5 μm.Palladium is preferred, to which silver or copper is particularly preferably added for the purpose of improving the hydrogen permeability and its mechanical properties while absorbing hydrogen in a concentration range of 15 to 25% by weight, preferably 20% by weight. The thickness of the metallic layer is 0.1 μm to 1000 μm, preferably less than 5 μm.
Die Auswahl der metallischen Schicht für die erfindungsgemäße Membran ist bevorzugt derart zu treffen, dass die Oberfläche der metallischen Schicht für die Synthesegasreaktion katalytisch genügend aktiv ist. Bei einer bevorzugten Ausführungsform können auf der Oberfläche hochaktive Katalysatorzentren zusätzlich aufgebracht werden, um die katalytische Aktivität zu erhöhen. Diese die Synthesegasreaktionen fordernden hochaktiven Katalysatoren werden in Form von submikrometerskaligen Dots mit einer Größe von 20 nm bis 1 μm, vorzugsweise 100 nm regelmäßig mit mittleren lateralen Abstanden von 0,1 μm bis 50 μm aufgebracht. Dabei kommen nachfolgend aufgeführte Materialen zum Einsatz:The selection of the metallic layer for the membrane according to the invention is preferably to be made such that the surface of the metallic layer is catalytically sufficiently active for the synthesis gas reaction. In a preferred embodiment, highly active catalyst centers can additionally be applied to the surface in order to increase the catalytic activity. These highly active catalysts which require the synthesis gas reactions are applied in the form of submicron-sized dots with a size of 20 nm to 1 μm, preferably 100 nm, regularly with average lateral distances of 0.1 μm to 50 μm. The following materials are used:
Als Katalysatoren für die Synthesegasreaktion können die Elemente Platin, Palladium, Rhodium, Rhenium, Nickel, Kupfer und/oder Kobalt verwendet werden. Diese Elemente können in der metallischen Form allein oder in Legierung mit anderen Metallen oder in
oxidierter oder reduzierte Form in katalytisch aktiven Verbindungen mit anderen Elementen eingesetzt werden.The elements platinum, palladium, rhodium, rhenium, nickel, copper and / or cobalt can be used as catalysts for the synthesis gas reaction. These elements can be in metallic form alone or in alloy with other metals or in oxidized or reduced form can be used in catalytically active compounds with other elements.
Bei einer bevorzugten Ausfuhrungsforn der Erfindung ist die Zusammensetzung der auf der Oberfläche der metallischen Schicht vorgesehenen Katalysatorzentren von der Zusammensetzung der metallischen Schicht verschieden.In a preferred embodiment of the invention, the composition of the catalyst centers provided on the surface of the metallic layer is different from the composition of the metallic layer.
Bei einer weiteren bevorzugten Ausführungsform kann die metallische Schicht der flexiblen Verbundmembran zum Ausgleich und/oder zur Vermeidung von Spannungen aufgrund von Volumenänderungen durch Wasserstoffaufiiahme ein Muster von sich abwechselnden konkaven und konvexen Bereichen aufweisen. Die Volumenänderungen treten immer dann auf, wemi Wasserstoff von der selektiven Schicht sorbiert wird, und dies ist im Trennprozess der Fall. Denn durch die Volumenänderung durch Wasserstoffaufnahme kommt es zu einer Veränderung der Oberfläche der Membran, die soweit gehen kann, dass sich Risse in der Membrane bilden, und dann mit dieser Membrane keine Trennung mehr möglich ist. Dieses Problem tritt umso stärker in den Vordergrund je dünner und empfindlicher die wasserstoffselektiven Schichten werden. Bei rohrförmigen Membranen tritt dies ebenfalls auf, ist aber nicht ganz so problematisch wie bei plattenformigen Systemen, da durch die Geometrie der rohrförmigen Bauform viele Spannungen abgefangen werden können. Das heißt, Veränderungen der Oberfläche treten bei rohrförmigen Membranen erst nach 10 mal mehr Zyklen auf als bei plattenformigen Membranen. Das Problem als solches ist aber nicht vernachlässigbar.In a further preferred embodiment, the metallic layer of the flexible composite membrane can have a pattern of alternating concave and convex regions in order to compensate and / or to avoid stresses due to volume changes due to hydrogen absorption. The volume changes always occur when hydrogen is sorbed by the selective layer, and this is the case in the separation process. Because the volume change due to hydrogen absorption leads to a change in the surface of the membrane, which can go so far that cracks form in the membrane, and then separation is no longer possible with this membrane. This problem comes to the fore the thinner and more sensitive the hydrogen-selective layers become. This also occurs with tubular membranes, but is not quite as problematic as with plate-shaped systems, since the geometry of the tubular design means that many stresses can be absorbed. This means that changes in the surface only occur after 10 times more cycles with tubular membranes than with plate-shaped membranes. But the problem as such is not negligible.
Die metallischen Schichten, die vorzugsweise ein Muster von sich abwechselnden konkaven und konvexen Bereichen aufweisen, können Spannungen, die aus Volumenänderungen der selektiven Schichten entstehen, besser auffangen and zeigen dadurch eine deutlich verbesserte Langzeitstabilität. Diese Spannungen werden durch die besondere Staiktur der metallischen Schicht auf der Trägermembran, die einen durchbrochenen Träger aufweist, gewährleistet. In diesem Fall führt die "gewellte" Struktur der Oberfläche mit "Hügeln" an den nicht durchbrochenen Stellen und "Tälern" an den durchbrochenen Stellen des durchbrochenen Trägers zu diesem Effekt. Dadurch, dass die gesamte Membrane eine "Berg- und
Tal-Struktur" in unregelmäßigen oder vorzugsweise regelmäßigen Abständen besitzt, d.h. eine Struktur mit abwechselnd konkaven und konvexen Bereichen, können durch die durch die Wasserstoffsorption induzierten Volumenänderungen besser abgebaut werden. Wichtiger Punkt ist dabei, dass die metallische Schicht nicht zu dick sein darf, so dass diese Vorteile durch den Nachteil einer zu großen Schichtdicke wieder aufgehoben werden. Idealerweise sollte die metallische Schicht weniger als 5 μm dick sein. Besonders bevorzugt dünner als 2 μm and ganz besonders bevorzugt weniger als 1 μm.The metallic layers, which preferably have a pattern of alternating concave and convex regions, can better absorb stresses that arise from changes in volume of the selective layers and thereby show a significantly improved long-term stability. These tensions are guaranteed by the special static of the metallic layer on the carrier membrane, which has a perforated carrier. In this case, the "corrugated" structure of the surface with "hills" at the uninterrupted areas and "valleys" at the open areas of the openwork support leads to this effect. The fact that the entire membrane is a "mountain and Valley structure "at irregular or preferably regular intervals, ie a structure with alternating concave and convex areas, can be degraded better by the volume changes induced by hydrogen sorption. An important point is that the metallic layer must not be too thick, so that these advantages are canceled out by the disadvantage of an excessively thick layer. Ideally, the metallic layer should be less than 5 μm thick, particularly preferably thinner than 2 μm and very particularly preferably less than 1 μm.
Bei einer weiteren bevorzugten Ausführungsform der Erfindung unterscheiden sich der thermische Ausdehnungskoeffizient der Trägermembran und der thermische Ausdehnungskoeffizient der metallischen Schicht um weniger als 15 %, vorzugsweise weniger als 10 %. Ganz besonders bevorzugt sind der thermische Ausdehnungskoeffizient der Trägermembran und der thermische Ausdehnungskoeffizient der Metallschicht in etwa gleich groß. Dies wird durch die geeignete Wahl des durchbrochenen Trägers gewährleistet, der vorzugsweise aus Metall besteht. So können Risse in der metallischen Schicht durch Temperaturänderungen vermieden werden.In a further preferred embodiment of the invention, the coefficient of thermal expansion of the carrier membrane and the coefficient of thermal expansion of the metallic layer differ by less than 15%, preferably less than 10%. The thermal expansion coefficient of the carrier membrane and the thermal expansion coefficient of the metal layer are very particularly preferably approximately the same size. This is ensured by the suitable choice of the openwork carrier, which is preferably made of metal. In this way, cracks in the metallic layer due to temperature changes can be avoided.
Die anwendungstechnischen Vorteile der Erfindung werden im Folgenden beschrieben.The application technology advantages of the invention are described below.
Die Oberfläche der erfindungsgemäßen Membran ist katalysatoraktiv. Die Synthesegasreaktion findet an der Oberfläche der wasserstoffspeichernden metallischen Schicht oder bei einer weiteren Ausführungsform der Erfindung auch an speziell aufgebrachten hochaktiven submikrometerskaligen Katalysator-Dots statt.The surface of the membrane according to the invention is active as a catalyst. The synthesis gas reaction takes place on the surface of the hydrogen-storing metallic layer or, in a further embodiment of the invention, also on specially applied, highly active, submicron-scale catalyst dots.
Die erfindungsgemäßen Membranen zur Erzeugung von hochreinem Wasserstoff aus dem Reforming-Prozess besitzen die Eigenschaft, Wasserstoff - üblicherweise atomar - bei hohem Wasserstoffgaspartialdruck in das kristalline Gefüge auf Zwischengitterplatzen bis zum Erreichen des chemischen Gleichgewichts zu deponieren. Wenn der Wasserstoffgaspartialdruck abgesenkt wird, wird das Gas wieder freigesetzt. Innerhalb des Membranreaktors herrscht bei Betrieb ein hoher Wasserstoffgasdruck. Außerhalb des Reaktors herrscht ein demgegenüber stark abgesenkter Wasserstoffdruck. Die metallische
Schicht, bestehend aus dem wasserstoffspeichernden Material, stellt somit eine geeignete Membran für die Abtrennung von hochreinen Wasserstoff dar.The membranes according to the invention for producing high-purity hydrogen from the reforming process have the property of depositing hydrogen — usually atomically — into the crystalline structure at interstitial sites at high hydrogen gas partial pressure until chemical equilibrium is reached. When the hydrogen gas partial pressure is reduced, the gas is released again. A high hydrogen gas pressure prevails within the membrane reactor during operation. In contrast, a greatly reduced hydrogen pressure prevails outside the reactor. The metallic Layer, consisting of the hydrogen-storing material, thus represents a suitable membrane for the separation of high-purity hydrogen.
Bei einer bevorzugten Ausführungsform der Erfindung umfasst der durchbrochene Träger des Verbundwerkstoffs der erfindungsgemäßen Verbundmembran ein Metallgewebe, vorzugsweise ein Edelstahlgewebe und/oder Edelstahl vlies. Das Metallgewebe kann leicht elektrisch kontaktiert werden, so dass mittels eines anzulegenden elektrischen Stroms Ohm'sche Wärme in unmittelbarer Nähe des Reaktionsgeschehens entsteht. Diese derart erzeugte Wärme gelangt an die katalytisch aktiven Bereiche der erfindungsgemäßen Membran und kann die für die Synthesegasreaktion notwendige endotherme Reaktionsenthalpie bereitstellen. Diese Art der Energiezufuhr gestattet eine gezielte Aufheizung der reaktiven Zentren, so dass Verluste durch die Aufheizung von Gasen im Inneren des Reaktors weitestgehend vermieden werden können. Die elektrische Beheizung kann innerhalb kürzester Zeit regelbar erfolgen. Die Erzeugung von Wasserstoff wird somit fein dosierbar regelbar. Diese Eigenschaft ist für die Belange des Brennstoffzellen-automobils von großem Vorteil, weil dadurch insbesondere Lastwechselvorgänge leicht beherrschbar werden. Darüber hinaus können Kaltstartphasen durch eine schnelle elektrische Aufheizung der reaktiven Zentren stark verkürzt werden.In a preferred embodiment of the invention, the perforated support of the composite material of the composite membrane according to the invention comprises a metal mesh, preferably a stainless steel mesh and / or stainless steel fleece. The metal mesh can be easily contacted electrically, so that an electrical current to be applied creates ohmic heat in the immediate vicinity of the reaction. This heat generated in this way reaches the catalytically active areas of the membrane according to the invention and can provide the endothermic reaction enthalpy required for the synthesis gas reaction. This type of energy supply allows targeted heating of the reactive centers, so that losses due to the heating of gases inside the reactor can be largely avoided. The electrical heating can be regulated in a very short time. The generation of hydrogen can thus be regulated in a finely adjustable manner. This property is of great advantage for the needs of the fuel cell automobile, because it makes it particularly easy to manage load change processes. In addition, cold start phases can be greatly shortened by rapid electrical heating of the reactive centers.
Die Rate der Wasserstoffbildung bei der Verwendung der erfindungsgemäßen Verbundmembran bei der Reformierung entspricht vorzugsweise im Wesentlichen der Rate des Wasserstoffdurchtritts durch die Verbundmembran.The rate of hydrogen formation when using the composite membrane according to the invention in the reforming preferably corresponds essentially to the rate of hydrogen passage through the composite membrane.
Die erfindungsgemäße Membran bietet aufgrund des durchbrochenen Trägers im Inneren eine genügend gute Stabilität insbesondere gegenüber dem hohen Druckunterschied zwischen dem Inneren and dem Äußeren des Reaktors.The membrane according to the invention offers sufficient stability due to the perforated support inside, in particular with respect to the high pressure difference between the inside and the outside of the reactor.
Der flexible, durchbrochene Träger der erfindungsgemäßen Verbundmembran kann einThe flexible, openwork support of the composite membrane according to the invention can be a
Material umfassen, das ausgewählt ist aus Glas, Mineralien, Kunststoffen, amorphen, nicht elektrisch leitenden Substanzen, Naturprodukten, Verbundstoffen, Verbundwerkstoffen oder aus zumindest einer Kombination dieser Materialien, vorausgesetzt, dass diese Materialien die
Brauchbarkeit der erfindungsgemäßen Verbundmembran unter den Betriebsbedingungen in einer Brennstoffzelle nicht beeinträchtigen. Als flexibler, durchbrochener Träger, kann auch ein Träger verwendet werden, der durch Behandlung mit Laserstrahlen, Ionenstrahlen oder einem Ätzmittel stoffdurchlässig gemacht wurde.Include material selected from glass, minerals, plastics, amorphous, non-electrically conductive substances, natural products, composites, composite materials or from at least a combination of these materials, provided that these materials the Do not impair the usability of the composite membrane according to the invention under the operating conditions in a fuel cell. A carrier which has been made permeable to matter by treatment with laser beams, ion beams or an etchant can also be used as a flexible, openwork carrier.
Der durchbrochene Träger umfasst vorzugsweise Fasern und/oder Filamente mit einem Durchmesser von 1 bis 150 μm, vorzugsweise 1 bis 20 μm, und/oder Fäden mit einem Durchmesser von 5 bis 150 μm, vorzugsweise 20 bis 70 μm, umfasst.The openwork carrier preferably comprises fibers and / or filaments with a diameter of 1 to 150 μm, preferably 1 to 20 μm, and / or threads with a diameter of 5 to 150 μm, preferably 20 to 70 μm.
Für den Fall, dass der durchbrochene Träger ein Gewebe ist, dann handelt es sich dabei vorzugsweise um ein Gewebe aus 11-Tex-Garnen mit 5 - 50 Kett- bzw. Schussfäden und insbesondere 20 - 28 Kett- und 28 - 36 Schussfäden. Ganz besonders bevorzugt werden 5,5-Tex Garne mit 10 - 50 Kett- bzw. Schussfaden und bevorzugt 20 - 28 Kett- und 28 - 36 Schussfäden.In the event that the openwork carrier is a woven fabric, then this is preferably a woven fabric made of 11-Tex yarns with 5-50 warp or weft threads and in particular 20-28 warp and 28-36 weft threads. 5,5-Tex yarns with 10-50 warp or weft threads are particularly preferred, and 20-28 warp and 28-36 weft threads are preferred.
Die erfindungsgemäße Verbundmembran kann vorzugsweise bei einer Temperatur zwischen 300 °C und 900 °C betrieben werden, besonders bevorzugt bei mehr als 500 °C, ganz besonders bevorzugt bei mehr als 800 °C.The composite membrane according to the invention can preferably be operated at a temperature between 300 ° C. and 900 ° C., particularly preferably at more than 500 ° C., very particularly preferably at more than 800 ° C.
Der Brennstoff, der bei der Verwendung der erfindungsgemäßen Verbundmembran in einem Membranreaktor zur Reformierung von Brennstoffen vorzugsweise eingesetzt wird, umfasst einen Kohlenwasserstoff oder einen Alkohol. Besonders bevorzugt umfasst der Brennstoff Methan, Ethan, Propan und/oder Butan oder Methanol und/oder Ethanol.The fuel which is preferably used when the composite membrane according to the invention is used in a membrane reactor for reforming fuels comprises a hydrocarbon or an alcohol. The fuel particularly preferably comprises methane, ethane, propane and / or butane or methanol and / or ethanol.
Bei einer bevorzugten Ausführungsform der Erfindung ist die metallische Schicht beheizbar. Ganz besonders bevorzugt ist die metallische Schicht durch eine Widerstandsheizung indirekt beheizbar.In a preferred embodiment of the invention, the metallic layer can be heated. The metallic layer is very particularly preferably indirectly heated by resistance heating.
Die erfindungsgemäße Verbundmembran wird vorzugsweise in einem Membranreaktor verwendet, der ein Reformer für eine Brennstoffzelle für stationäre oder mobile Anwendungen ist.
Bei einer bevorzugten Ausführungsform kann eine erfindungsgemäße Verbundmembran in einem Membranreaktor bei einem Druck von 0,5 bis 200 bar (0,5 bis 200 x 105 Pa) betrieben werden.The composite membrane according to the invention is preferably used in a membrane reactor which is a reformer for a fuel cell for stationary or mobile applications. In a preferred embodiment, a composite membrane according to the invention can be operated in a membrane reactor at a pressure of 0.5 to 200 bar (0.5 to 200 × 10 5 Pa).
Im Folgenden wird die Herstellung der erfindungsgemäßen Verbundmembranen beschrieben.The production of the composite membranes according to the invention is described below.
Die erfindungsgemäße Verbundmembran ist erhältlich durchThe composite membrane according to the invention is obtainable from
(A) Hydrolyse einer hydrolysierbaren Metallverbindung zu einem Hydrolysat,(A) hydrolysis of a hydrolyzable metal compound to a hydrolyzate,
(B) Peptisierung des Hydrolysats mit einer Säure zu einer Dispersion, (C) Vermischen der Dispersion mit einem nanokristallinen und/oder kristallinen Metalloxid,(B) peptizing the hydrolyzate with an acid to form a dispersion, (C) mixing the dispersion with a nanocrystalline and / or crystalline metal oxide,
(D) Aufbringen, der unter (C) erhaltenen Mischung als dünne Schicht auf einen durchbrochenen Träger, vorzugsweise ein Gewebe und/oder ein Vlies, und(D) applying the mixture obtained under (C) as a thin layer to an openwork support, preferably a fabric and / or a nonwoven, and
(E) Verfestigen bei einer Temperatur von etwa 100 °C, um einen Verbundstoff zu schaffen sowie(E) Solidify at a temperature of about 100 ° C to create a composite as well
(F) gegebenenfalls Wiederholung der Schritte (A) bis (E) mit dem Verbundstoff aus Stufe (E) unter Anwendung von Mischungen, die Teilchen mit geringerer Teilchengröße enthalten, um einen mehrschichtigen Verbundstoff zu schaffen.(F) optionally repeating steps (A) through (E) with the composite from step (E) using mixtures containing particles of smaller particle size to create a multilayer composite.
Als Dispersionen können handelsübliche Sole, wie Titannitratsol, Zirkonnitratsol oder Silikasol oder ein Sol von Aluminiumoxid eingesetzt werden.Commercially available sols such as titanium nitrate sol, zirconium nitrate sol or silica sol or a sol of aluminum oxide can be used as dispersions.
Die Dispersionen sind aber auch erhältlich durch Hydrolyse einer Metallverbindung, Halbmetallverbindung oder Mischmetallverbindung in einem Medium, wie Wasser, Alkohol oder einer Säure. Als zu hydrolisierende Verbindung wird vorzugsweise ein Metallnitrat, ein Metallchlorid, ein Metallcarbonat, eine Metallalkoholatverbindung oder eine Halbmetallalkoholatverbindung, besonders bevorzugt zumindest eineHowever, the dispersions can also be obtained by hydrolysis of a metal compound, semimetal compound or mixed metal compound in a medium, such as water, alcohol or an acid. The compound to be hydrolyzed is preferably a metal nitrate, a metal chloride, a metal carbonate, a metal alcoholate compound or a semimetal alcoholate compound, particularly preferably at least one
Metallalkoholatverbindung, ein Metallnitrat, ein Metallchlorid, ein Metallcarbonat oder zumindest eine Halbmetallalkoholatverbindung ausgewählt aus den Verbindungen der Elemente Ti, Zr, AI, Si, Sn, Ce and Y oder der Lanthanoiden and Actinoiden, wie z. B. Titanalkoholate, wie z. B. Titanisopropylat, Siliziumalkoholate, Zirkoniumalkoholate, oder
ein Metallnitrat, wie z. B. Zirkoniumnitrat, hydrolisiert. Es kann vorteilhaft sein, die Hydrolyse mit mindestens dem halben Molverhältnis an Wasser, bezogen auf die hydrolisierbare Gruppe der hydrolisierbaren Verbindung, durchzuführen.Metal alcoholate compound, a metal nitrate, a metal chloride, a metal carbonate or at least a semimetal alcoholate compound selected from the compounds of the elements Ti, Zr, Al, Si, Sn, Ce and Y or the lanthanoids and actinides, such as, for. B. titanium alcoholates such. B. titanium isopropylate, silicon alcoholates, zirconium alcoholates, or a metal nitrate, such as B. zirconium nitrate hydrolyzed. It may be advantageous to carry out the hydrolysis with at least half the molar ratio of water, based on the hydrolyzable group of the hydrolyzable compound.
Die hydrolisierte Verbindung kann mit einer Säure, vorzugsweise mit einer 10 bis 60%igen Säure, bevorzugt mit einer Mineralsäure, ausgewählt aus Schwefelsäure, Salzsäure, Perchlorsäure, Phosphorsäure and Salpetersäure oder einer Mischung dieser Säuren peptisiert werden.The hydrolyzed compound can be peptized with an acid, preferably with a 10 to 60% acid, preferably with a mineral acid selected from sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid and nitric acid or a mixture of these acids.
Eine anorganische Komponente mit einer Korngröße von 1 bis 10 000 nm kann in dem Sol suspendiert werden. Vorzugsweise wird eine anorganische Komponente, die eine Verbindung, ausgewählt aus Metallverbindungen, Halbmetallverbindungen, Mischmetallverbindungen und Metallmischverbindungen mit zumindest einem der Elemente der 3. bis 7. Hauptgruppe, oder zumindest eine Mischung dieser Verbindungen aufweist, suspendiert. Besonders bevorzugt wird zumindest eine anorganische Komponente, die zumindest eine Verbindung aus den Oxiden der Nebengruppenelemente oder den Elementen der 3. bis 5. Hauptgruppe, vorzugsweise Oxide, ausgewählt aus den Oxiden der Elemente Sc, Y, Ti, Zr, Nb, Ce, V, Cr, Mo, W, Mn, Fe, Co, B, AI, In, TI, Si, Ge, Sn, Pb and Bi, wie z. B. Y2O3, ZrO2, Fe2O3, Fe3O4, SiO2, Al2O3, aufweist, suspendiert. Die anorganische Komponente kann auch Alumosilicate, Aluminiumphospate, Zeolithe oder partiell ausgetauschte Zeolithe, wie z. B. ZSM-5, Na-ZSM-5 oder Fe-ZSM-5 oder amorphe mikroporöse Mischoxide, die bis zu 20 % nicht hydrolisierbare organische Verbindungen enthalten können, wie z. B. Vanadinoxid, Siliziumoxid-Glas oder Aluminiumoxid- Siliciumoxid- Methylsiliciumsesquioxid-Gläser, aufweisen.An inorganic component with a grain size of 1 to 10,000 nm can be suspended in the sol. An inorganic component which has a compound selected from metal compounds, semimetal compounds, mixed metal compounds and mixed metal compounds with at least one of the elements of the 3rd to 7th main group, or at least a mixture of these compounds, is preferably suspended. Particular preference is given to at least one inorganic component which comprises at least one compound from the oxides of the subgroup elements or from the elements of the 3rd to 5th main group, preferably oxides, selected from the oxides of the elements Sc, Y, Ti, Zr, Nb, Ce, V , Cr, Mo, W, Mn, Fe, Co, B, AI, In, TI, Si, Ge, Sn, Pb and Bi, such as B. Y 2 O 3 , ZrO 2 , Fe 2 O 3 , Fe 3 O 4 , SiO 2 , Al 2 O 3 , suspended. The inorganic component can also be aluminosilicates, aluminum phosphates, zeolites or partially exchanged zeolites, such as, for. B. ZSM-5, Na-ZSM-5 or Fe-ZSM-5 or amorphous microporous mixed oxides, which can contain up to 20% non-hydrolyzable organic compounds, such as. B. vanadium oxide, silicon oxide glass or aluminum oxide-silicon oxide-methyl silicon sesquioxide glasses.
Vorzugsweise beträgt der Massenanteil der suspendierten Komponente das 0,1 bis 500fache der eingesetzten hydrolisierten Verbindung.The mass fraction of the suspended component is preferably 0.1 to 500 times the hydrolyzed compound used.
Durch geeignete Wahl der Korngröße der suspendierten Verbindungen in Abhängigkeit von der Größe der Poren, Löcher oder Zwischenräume des Trägers, aber auch durch geeignete
Wahl der Schichtdicke des Verbundwerkstoffes sowie des anteiligen Verhältnisses von Sol : Lösungsmittel : Metalloxid lassen sich Risse im Verbundwerkstoff vermeiden.Through a suitable choice of the grain size of the suspended compounds depending on the size of the pores, holes or interstices of the carrier, but also through suitable ones Choice of the layer thickness of the composite material and the proportionate ratio of sol: solvent: metal oxide can avoid cracks in the composite material.
Das Metalloxid, das in Schritt (C) mit der Dispersion vermischt wird, ist vorzugsweise ausgewählt aus der Gruppe, bestehend aus Titanoxid, Aluminiumoxid, Siliciumoxid und Zirkonoxid oder aus deren Mischoxiden und die hydrolysierbare Metallverbindung ist vorzugsweise eine Verbindung von Titan, Zirkonium, Silizium, oder Aluminium.The metal oxide which is mixed with the dispersion in step (C) is preferably selected from the group consisting of titanium oxide, aluminum oxide, silicon oxide and zirconium oxide or from their mixed oxides and the hydrolyzable metal compound is preferably a compound of titanium, zirconium, silicon, or aluminum.
Bei Verwendung eines Maschengewebes mit einer Maschenweite von z. B. 100 μm als durchbrochenen Träger können zur Erhöhung der Rissfreiheit vorzugsweise Mischungen verwendet werden, die eine suspendierte Verbindung mit einer Korngröße von mindestensWhen using a mesh fabric with a mesh size of z. B. 100 microns as an openwork carrier can preferably be used to increase the freedom from cracks, the suspended compound with a grain size of at least
0,7 μm aufweist. Im Allgemeinen sollte das Verhältnis Korngröße zu Maschen- bzw.0.7 μm. In general, the ratio of grain size to mesh or
Porengröße von 1:1000 bis 50:1000 betragen. Der Verbundwerkstoff kann vorzugsweise einePore size from 1: 1000 to 50: 1000. The composite material can preferably be a
Dicke von 5 bis 1000 μm, besonders bevorzugt von 50 bis 150 μm, aufweisen. Die Mischung aus Dispersion und zu suspendierenden Verbindungen weist vorzugsweise ein VerhältnisThickness from 5 to 1000 microns, particularly preferably from 50 to 150 microns. The mixture of dispersion and compounds to be suspended preferably has a ratio
Dispersion zu suspendierenden Verbindungen von 0,1:100 bis 100:0,1, vorzugsweise vonDispersion compounds to be suspended from 0.1: 100 to 100: 0.1, preferably from
0,1:10 bis 10:0,1 Gewichtsteilen auf.0.1: 10 to 10: 0.1 parts by weight.
Die Mischung kann nach Aufbringen auf dem durchbrochenen Träger durch Erwärmen des Verbundes aus Mischung und durchbrochenen Träger auf 50 bis 1000 °C, vorzugsweise etwa 100 °C verfestigt werden. In einer besonderen Ausführungsform wird der Verbund für 10 Minuten bis 5 Stunden einer Temperatur von 50 bis 100 °C ausgesetzt. In einer weiteren besonderen Ausführungsform wird der Verbund für 1 Sekunde bis 10 Minuten einer Temperatur von 100 bis 800 °C ausgesetzt. Das Erwärmen des Verbundes kann mit erwärmter Luft, Heißluft, Infrarotstrahlung, Mikrowellenstrahlung oder elektrisch erzeugter Wärme, erfolgen. In einer weiteren Ausfuhrungsform kann das Verfestigen der Mischung dadurch erreicht werden, dass die Mischung auf einen vorgewärmten Träger aufgebracht wird und somit sofort nach dem Aufbringen verfestigt wird.After application to the openwork carrier, the mixture can be solidified by heating the composite of mixture and openwork carrier to 50 to 1000 ° C., preferably about 100 ° C. In a particular embodiment, the composite is exposed to a temperature of 50 to 100 ° C. for 10 minutes to 5 hours. In a further particular embodiment, the composite is exposed to a temperature of 100 to 800 ° C. for 1 second to 10 minutes. The composite can be heated with heated air, hot air, infrared radiation, microwave radiation or electrically generated heat. In a further embodiment, the mixture can be solidified by the mixture being applied to a preheated carrier and thus being solidified immediately after the application.
In einer weiteren besonderen Ausführungsform wird der durchbrochene Träger von einer Rolle abgerollt mit einer Geschwindigkeit von 1 m/h bis 1 m/s, auf eine Apparatur, die die
Mischung mit dem Träger kontaktiert und anschließend zu einer weiteren Apparatur, die das Verfestigen der Mischung durch Erwärmen ermöglicht, und der so hergestellte Verbundwerkstoff wird auf einer zweiten Rolle aufgerollt. Auf diese Weise ist es möglich, den Verbundwerkstoff kontinuierlich herzustellen.In a further particular embodiment, the perforated carrier is rolled off a roll at a speed of 1 m / h to 1 m / s, on an apparatus which Contacted mixture with the carrier and then to another apparatus that allows the mixture to solidify by heating, and the composite material thus produced is rolled up on a second roll. In this way it is possible to manufacture the composite material continuously.
In einer weiteren Ausführungsform wird auf einen Verbundwerkstoff, eine keramische oder anorganische Schicht aufgebracht. Dies kann beispielsweise dadurch erfolgen, dass eine grüne (ungesinterte) Keramikschicht oder eine anorganische Schicht, die auf einer Hilfsfolie vorliegt, auf den Träger auflaminiert wird oder dass der Verbundwerkstoff mit einer weiteren Suspension (Mischung) wie oben besclirieben behandelt wird. Dieser Verbund kann durch Aufheizen verfestigt werden. Die verwendete grüne Keramikschicht enthält vorzugsweise ein nanokristallines Pulver eines Halbmetall- oder Metalloxids, wie z. B. Aluminiumoxid, Titandioxid oder Zirkoniumdioxid. Die grüne Schicht kann einen organischen Binder enthalten.In a further embodiment, a ceramic or inorganic layer is applied to a composite material. This can be done, for example, by laminating a green (unsintered) ceramic layer or an inorganic layer, which is present on an auxiliary film, onto the carrier or by treating the composite material with a further suspension (mixture) as described above. This bond can be solidified by heating. The green ceramic layer used preferably contains a nanocrystalline powder of a semimetal or metal oxide, such as. As aluminum oxide, titanium dioxide or zirconium dioxide. The green layer can contain an organic binder.
Durch die Verwendung einer grünen Keramikschicht ist es auf einfache Weise möglich den Verbundwerkstoff mit einer zusätzlichen keramischen Schicht auszustatten, die je nach verwendeter Größe des nanokristallinen Pulvers, die Porosität des so hergestellten Verbundwerkstoffes bestimmt.By using a green ceramic layer, it is possible in a simple manner to equip the composite material with an additional ceramic layer which, depending on the size of the nanocrystalline powder used, determines the porosity of the composite material produced in this way.
Durch das Aufbringen zumindest einer weiteren anorganischen Schicht oder Keramikschicht erhält man einen Verbundwerkstoff, der einen Porengradienten aufweist. Zudem ist es durch mehrmaliges Aufbringen einer Schicht möglich, zur Herstellung von Verbundwerkstoffen mit einer bestimmten Porengröße auch solche Träger zu verwenden, deren Poren- bzw. Maschenweite zur Herstellung eines Verbundwerkstoffes mit der geforderten Porengröße nicht geeignet ist. Dies kann z. B. der Fall sein, wenn ein Verbundwerkstoff mit einer Porengröße von 0,25 μm unter Verwendung eines Trägers mit einer Maschenweite von über 300 μm hergestellt werden soll. Zum Erhalt eines solchen Verbundwerkstoffes kann es vorteilhaft sein, auf den Träger zuerst zumindest eine Suspension zu bringen, die geeignet ist Träger mit einer Maschenweite von 300 μm zu behandeln, und diese Suspension nach dem Aufbringen zu verfestigen. Der auf diese Weise erhaltene Verbundwerkstoff kann nun als
Trägermembran mit einer geringeren Maschen- bzw. Porengröße eingesetzt werden. Auf diese Trägermembran kann eine weitere Suspension aufgebracht werden, die eine Verbindung mit einer Korngröße von 0,5 μm aufweist.By applying at least one further inorganic layer or ceramic layer, a composite material is obtained which has a pore gradient. In addition, by applying a layer several times, it is also possible to use supports for the production of composite materials with a specific pore size, the pore or mesh size of which is not suitable for producing a composite material with the required pore size. This can e.g. B. be the case when a composite material with a pore size of 0.25 microns is to be produced using a carrier with a mesh size of over 300 microns. To obtain such a composite material, it may be advantageous to first bring at least one suspension onto the carrier which is suitable for treating carriers with a mesh size of 300 μm, and to solidify this suspension after application. The composite material obtained in this way can now be used as Support membrane with a smaller mesh or pore size can be used. A further suspension can be applied to this carrier membrane, which has a compound with a grain size of 0.5 μm.
Die Rissunempfindlichkeit bei Verbundwerkstoffen mit großen Maschen- bzw. Porenweiten kann auch dadurch verbessert werden, dass Suspensionen auf den Träger aufgebracht werden, die zumindest zwei suspendierte Verbindungen aufweisen. Vorzugsweise werden zu suspendierende Verbindungen verwendet, die ein Korngrößenverhältnis von 1:1 bis 1:20, besonders bevorzugt von 1 : 1,5 bis 1 : 2,5 aufweisen. Der Gewichtsanteil von der Korngrößenfraktion mit der kleineren Korngröße sollte einen Anteil von höchstens 50 %, vorzugsweise von 20 % and ganz besonders bevorzugt von 10 %, an dem Gesamtgewicht der eingesetzten Komgrößenfraktion nicht überschreiten.The insensitivity to cracks in composite materials with large mesh or pore widths can also be improved by applying suspensions to the carrier which have at least two suspended compounds. Compounds to be suspended are preferably used which have a particle size ratio of 1: 1 to 1:20, particularly preferably 1: 1.5 to 1: 2.5. The weight fraction of the grain size fraction with the smaller grain size should not exceed a proportion of at most 50%, preferably 20% and very particularly preferably 10%, of the total weight of the grain size fraction used.
Bei einer bevorzugten Ausführungsform der Erfindung ist zwischen dem durchbrochenen Träger und der metallischen Schicht eine Wasserstoff durchlässige haftvermittelnde Schicht vorgesehen.In a preferred embodiment of the invention, a hydrogen-permeable adhesion-promoting layer is provided between the perforated support and the metallic layer.
Vorzugsweise ist die Verbundmembran elastisch und toleriert vorzugsweise einen Biegeradius bis herab zu 100 m vorzugsweise bis herab zu 10 cm und toleriert besonders bevorzugt einen maximalen Biegeradius im Bereich von 1 bis 100 mm auf, ohne dass die auf Druck beanspruchte metallische Schicht Risse bildet.The composite membrane is preferably elastic and preferably tolerates a bending radius down to 100 m, preferably down to 10 cm, and particularly preferably tolerates a maximum bending radius in the range from 1 to 100 mm without the metallic layer subjected to pressure forming cracks.
Die erfmdungsgemäße Verbundmembran ist vorzugsweise eine asymmetrische Verbundmembran.The composite membrane according to the invention is preferably an asymmetrical composite membrane.
Das Aufbringen der metallischen Schicht auf die Trägermembran erfolgt durch bekannte Beschichtungsverfahren, wie CVD (chemical vapor deposition); PVD (physical vapor deposition, insbesondere Sputtering oder Plasmabeschichtung); Galvanische Abscheidung oder durch die stromlose Abscheidung (electroless plating). Diese Verfahren sind geeignet wasserstoffselektive und katalytisch aktive Schichten in guter Qualität auf den Trägermembranen aufzubringen.
Das Aufbringen der Katalysatorzentren (Dots) auf der metallischen Schicht erfolgt vorzugsweise durch Aufsprühen einer Suspension, welche die katalysatoraktive Komponente erhält.The metallic layer is applied to the carrier membrane by known coating methods, such as CVD (chemical vapor deposition); PVD (physical vapor deposition, in particular sputtering or plasma coating); Electroplating or electroless plating. These processes are suitable for applying hydrogen-selective and catalytically active layers in good quality to the support membranes. The catalyst centers (dots) are preferably applied to the metallic layer by spraying on a suspension which contains the catalyst-active component.
Das Aufbringen der Katalysatorzentren (Dots) kann aber auch nach den gleichen Verfahren erfolgen wie das Aufbringen der metallischen Schicht auf der Trägermembran. Zuvor wird jedoch ein rasterförmiges Muster auf der Metallschicht aufgebracht. Die Katalysatorzentren werden dann in den Zwischenräumen des Rasters, in den durch das Raster vorbestimmten Abständen, auf der Metallschicht aufgebracht. Danach wird das Raster vorzugsweise wieder entfernt. Sofern das Raster wasserstoffdurchlässig und für die Reformierung inert ist und die katalytische Aktivität der Katalysatorzentren ausreichend ist, kann das Raster aber auch auf der metallischen Schicht verbleiben.The catalyst centers (dots) can, however, also be applied by the same methods as the application of the metallic layer on the support membrane. Before that, however, a grid-like pattern is applied to the metal layer. The catalyst centers are then applied to the metal layer in the spaces between the grid, at the intervals predetermined by the grid. The grid is then preferably removed again. If the grid is permeable to hydrogen and inert to the reforming and the catalytic activity of the catalyst centers is sufficient, the grid can also remain on the metallic layer.
Die vorliegende Erfindung stellt auch einen Membranreaktor bereit, der eine erfindungsgemäße Verbundmembran umfasst. Vorzugsweise wird der Membranreaktor kontinuierlich betrieben.
The present invention also provides a membrane reactor comprising a composite membrane according to the invention. The membrane reactor is preferably operated continuously.
Claims
1. Verwendung einer flexiblen, porösen Membran als Trägermembran in einer elektrisch beheizbaren Verbundmembran für einen Membranreaktor in dem durch Reformierung von Brennstoffen Wasserstoff erzeugt wird, wobei die Verbundmembran die Trägermembran und eine die Reformierung katalysierende metallische Schicht umfasst und zur selektiven Abtrennung des erzeugten Wasserstoffs aus dem Membranreaktor dient.1. Use of a flexible, porous membrane as a carrier membrane in an electrically heatable composite membrane for a membrane reactor in which hydrogen is produced by reforming fuels, the composite membrane comprising the carrier membrane and a metallic layer catalyzing the reforming and for the selective separation of the hydrogen generated from the Membrane reactor is used.
2. Verwendung einer flexiblen, porösen Membran in einem Membranreaktor in dem durch Reformierung von Brennstoffen Wasserstoff erzeugt wird, als Trägermembran in einer elektrisch beheizbaren Verbundmembran, die die Trägermembran und eine die Reformierung katalysierende metallische Schicht umfasst und die zur selektiven Abtrennung des erzeugten Wasserstoffs aus dem Membranreaktor dient.2. Use of a flexible, porous membrane in a membrane reactor in which hydrogen is produced by reforming fuels, as a carrier membrane in an electrically heatable composite membrane, which comprises the carrier membrane and a metallic layer catalyzing the reforming and which selectively separates the hydrogen generated from the Membrane reactor is used.
3. Verwendung nach Anspruch 2, dadurch gekennzeichnet, dass der Membranreaktor bei einem Druck von 0,5 bis 200 bar (0,5 bis 200 x 105 Pa) betrieben wird.3. Use according to claim 2, characterized in that the membrane reactor is operated at a pressure of 0.5 to 200 bar (0.5 to 200 x 10 5 Pa).
4. Verwendung nach einem der Ansprüche 2 oder 3, wobei die Verbundmembran bei einer Temperatur von mehr als 300 °C betrieben wird.4. Use according to one of claims 2 or 3, wherein the composite membrane is operated at a temperature of more than 300 ° C.
5. Verwendung nach einem der Ansprüche 2 bis 4, wobei der Membranreaktor kontinuierlich betrieben wird.5. Use according to one of claims 2 to 4, wherein the membrane reactor is operated continuously.
6. Verwendung nach Anspruch 5, wobei die Rate der Wasserstofϊbildung bei der Reformierung im Wesentlichen der Rate des Wasserstoffdurchtritts durch die Verbundmembran entspricht.6. Use according to claim 5, wherein the rate of hydrogen formation in the reforming substantially corresponds to the rate of hydrogen passage through the composite membrane.
7. Verwendung nach einem der Ansprüche 2 bis 6, wobei der Brennstoff einen Kohlenwasserstoff oder einen Alkohol umfasst. 7. Use according to any one of claims 2 to 6, wherein the fuel comprises a hydrocarbon or an alcohol.
8. Verwendung nach Anspruch 7, wobei der Brennstoff Methan, Ethan, Propan, Butan oder ein Gemisch davon oder Methanol oder Ethanol oder ein Gemisch davon umfasst.8. Use according to claim 7, wherein the fuel comprises methane, ethane, propane, butane or a mixture thereof or methanol or ethanol or a mixture thereof.
9. Verwendung nach Anspruch 1 bis 8, dadurch gekennzeichnet, dass die metallische Schicht beheizbar ist.9. Use according to claim 1 to 8, characterized in that the metallic layer is heatable.
10. Verwendung nach Anspruch 9, dadurch gekennzeichnet, dass die metallische Schicht durch eine Widerstandsheizung indirekt beheizbar ist.10. Use according to claim 9, characterized in that the metallic layer is indirectly heated by a resistance heater.
11. Verwendung nach einem der Ansprüche 1 bis 10, wobei der Membranreaktor ein Reformer für eine Brennstoffzelle für stationäre oder mobile Anwendungen ist.11. Use according to one of claims 1 to 10, wherein the membrane reactor is a reformer for a fuel cell for stationary or mobile applications.
12. Elektrisch beheizbare Verbundmembran, umfassend eine flexible, poröse Trägermembran und eine metallische Schicht, dadurch gekennzeichnet, dass (a) die flexible, poröse Trägermembran ein Verbundstoff ist, der einen durchbrochenen12. Electrically heatable composite membrane, comprising a flexible, porous carrier membrane and a metallic layer, characterized in that (a) the flexible, porous carrier membrane is a composite that has an openwork
Träger, vorzugsweise ein Gewebe und/oder Vlies sowie ein poröses Keramikmaterial umfasst, (b) die metallische Schicht geeignet istCarrier, preferably a fabric and / or nonwoven and a porous ceramic material, (b) the metallic layer is suitable
(bl) eine Reaktion zu katalysieren, bei der Wasserstoff gebildet wird, wenn die Verbundmembran mit einem Gemisch aus Methan und Wasser bei einer(bl) to catalyze a reaction in which hydrogen is formed when the composite membrane is mixed with a mixture of methane and water at a
Temperatur von 700 °C kontaktiert wird, sowie (b2) gebildeten Wasserstoff selektiv abzutrennen und andere Bestandteile des Reaktionsgemisches zurückzuhalten.Temperature of 700 ° C is contacted, and (b2) selectively separate hydrogen formed and retain other components of the reaction mixture.
13. Verbundmembran nach Anspruch 12, wobei die metallische Schicht Palladium oder Legierungen davon umfasst.13. The composite membrane of claim 12, wherein the metallic layer comprises palladium or alloys thereof.
14. Verbundmembran nach Anspruch 13, wobei die metallische Schicht eine Legierung aus Palladium mit Silber und oder Kupfer ist, vorzugsweise mit einer Zusammensetzung von14. The composite membrane according to claim 13, wherein the metallic layer is an alloy of palladium with silver and or or copper, preferably with a composition of
75 bis 85 Gew.-% Palladium und 15 bis 25 Gew.-% Silber oder Kupfer. 75 to 85% by weight of palladium and 15 to 25% by weight of silver or copper.
15. Verbundmembran nach Anspruch 13 oder 14, wobei die metallische Schicht zusätzlich Silber, Gold, Kupfer, Kobalt, Nickel, Ruthenium, Rhodium, Zink, Aluminium, Titan, Indium, Vanadium, Wolfram, Rhenium, Wolfram, Molybdän und/oder Seltenerdmetalle umfasst.15. The composite membrane according to claim 13 or 14, wherein the metallic layer additionally comprises silver, gold, copper, cobalt, nickel, ruthenium, rhodium, zinc, aluminum, titanium, indium, vanadium, tungsten, rhenium, tungsten, molybdenum and / or rare earth metals ,
16. Verbundmembran nach einem der Ansprüche 12 bis 15, wobei auf der Oberfläche der nicht-porösen Schicht Katalysatorzentren vorgesehen sind deren Zusammensetzung von der Zusammensetzung der Schicht verschieden ist.16. A composite membrane according to any one of claims 12 to 15, wherein catalyst centers are provided on the surface of the non-porous layer, the composition of which is different from the composition of the layer.
17. Verbundmembran nach Anspruch 16, wobei die Katalysatorzentren eine Größe im Bereich von 20 nm bis 1 μm, vorzugsweise 50 bis 150 nm aufweisen.17. The composite membrane according to claim 16, wherein the catalyst centers have a size in the range from 20 nm to 1 μm, preferably 50 to 150 nm.
18. Verbundmembran nach einem der Ansprüche 12 bis 17, wobei die Katalysatorzentren auf der Oberfläche der metallischen Schicht in einem mittleren lateralen Abstand von 0,1 bis 50 μm voneinander vorliegen.18. A composite membrane according to any one of claims 12 to 17, wherein the catalyst centers on the surface of the metallic layer are at an average lateral distance of 0.1 to 50 microns from each other.
19. Verbundmembran nach einem der Ansprüche 12 bis 18, wobei die metallische Schicht eine Dicke im Bereich von 0,1 bis 1000 μm, vorzugsweise weniger als 5 μm aufweist.19. Composite membrane according to one of claims 12 to 18, wherein the metallic layer has a thickness in the range of 0.1 to 1000 microns, preferably less than 5 microns.
20. Verbundmembran nach einem der Ansprüche 12 bis 19, wobei der durchbrochene Träger Metall, Glas, Kohle und/oder Keramik umfasst.20. Composite membrane according to one of claims 12 to 19, wherein the perforated support comprises metal, glass, coal and / or ceramic.
21. Verbundmembran nach Anspruch 20, wobei der Träger Edelstahl umfasst.21. The composite membrane of claim 20, wherein the carrier comprises stainless steel.
22. Verbundmembran nach einem der Ansprüche 12 bis 21, wobei der durchbrochene Träger Fasern und/oder Filamente mit einem Durchmesser von 1 bis 150 μm, vorzugsweise 1 bis 20 μm, und/oder Fäden mit einem Durchmesser von 5 bis 150 μm, vorzugsweise 20 bis 70 μm, umfasst.22. Composite membrane according to one of claims 12 to 21, wherein the perforated support fibers and / or filaments with a diameter of 1 to 150 microns, preferably 1 to 20 microns, and / or threads with a diameter of 5 to 150 microns, preferably 20 up to 70 μm.
23. Verbundmembran nach Anspruch 21 oder 22, wobei der durchbrochene Träger zur indirekten Widerstandsbeheizung der metallischen Schicht geeignet ist. 23. A composite membrane according to claim 21 or 22, wherein the perforated support is suitable for indirect resistance heating of the metallic layer.
24. Verbundmembran nach einem der Ansprüche 12 bis 23, wobei der Verbundstoff erhältlich ist durch24. The composite membrane according to any one of claims 12 to 23, wherein the composite is obtainable by
(A) Hydrolyse einer hydro lysierbaren Metallverbindung zu einem Hydrolysat,(A) hydrolysis of a hydrolyzable metal compound to a hydrolyzate,
(B) Peptisierung des Hydrolysats mit einer Säure zu einer Dispersion, (C) Vermischen der Dispersion mit einem nanokristallinen und/oder kristallinen(B) peptizing the hydrolyzate with an acid to form a dispersion, (C) mixing the dispersion with a nanocrystalline and / or crystalline
Metalloxid,metal oxide,
(D) Aufbringen, der unter (C) erhaltenen Mischung als dünne Schicht auf einen durchbrochenen Träger, vorzugsweise ein Gewebe und/oder ein Vlies, und(D) applying the mixture obtained under (C) as a thin layer to an openwork support, preferably a fabric and / or a nonwoven, and
(E) Verfestigen bei einer Temperatur von etwa 100 °C, um einen Verbundstoff zu schaffen sowie(E) Solidify at a temperature of about 100 ° C to create a composite as well
(F) gegebenenfalls Wiederholung der Schritte (A) bis (E) mit dem Verbundstoff aus Stufe (E) unter Anwendung von Mischungen, die Teilchen mit geringerer Teilchengröße enthalten, um einen mehrschichtigen Verbundstoff zu schaffen.(F) optionally repeating steps (A) through (E) with the composite from step (E) using mixtures containing particles of smaller particle size to create a multilayer composite.
25. Verbundmembran nach Anspruch 24, dadurch gekennzeiclmet, dass das Metalloxid ausgewählt ist aus der Gruppe, bestehend aus Titanoxid, Aluminiumoxid, Siliciumoxid und Zirkonoxid oder aus deren Mischoxiden und die Metallverbindung eine Verbindung von Titan, Zirkonium, Silizium, oder Aluminium ist.25. The composite membrane according to claim 24, characterized gekennzeiclmet that the metal oxide is selected from the group consisting of titanium oxide, aluminum oxide, silicon oxide and zirconium oxide or from their mixed oxides and the metal compound is a compound of titanium, zirconium, silicon, or aluminum.
26. Verbundmembran nach einem der Ansprüche 12 bis 25, wobei der Träger eine Dicke im Bereich von 10 bis 1000 μm, vorzugsweise 20 bis 200 μm, aufweist.26. Composite membrane according to one of claims 12 to 25, wherein the carrier has a thickness in the range of 10 to 1000 microns, preferably 20 to 200 microns.
27. Verbundmembran nach einem der Ansprüche 12 bis 26, wobei zwischen dem durchbrochenen Träger und der metallischen Schicht eine Wasserstoff durchlässige haftvermittelnde Schicht vorgesehen ist.27. Composite membrane according to one of claims 12 to 26, wherein a hydrogen-permeable adhesion-promoting layer is provided between the perforated support and the metallic layer.
28. Verbundmembran nach einem der Ansprüche 12 bis 27, wobei die Verbundmembran elastisch ist und einen maximalen Biegeradius im Bereich von 1 bis 100 mm aufweist ohne dass die auf Druck beanspruchte metallische Schicht Risse bildet.28. Composite membrane according to one of claims 12 to 27, wherein the composite membrane is elastic and has a maximum bending radius in the range of 1 to 100 mm without the metallic layer which is subjected to pressure forming cracks.
29. Verbundmembran nach einem der Ansprüche 12 bis 28, die eine asymmetrische Verbundmembran ist.29. Composite membrane according to one of claims 12 to 28, which is an asymmetrical Composite membrane is.
30. Membranreaktor, umfassend die katalytische Verbundmembran nach einem der Ansprüche 12 bis 29. 30. membrane reactor comprising the catalytic composite membrane according to any one of claims 12 to 29.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10122888.0 | 2001-05-11 | ||
| DE10122888A DE10122888A1 (en) | 2001-05-11 | 2001-05-11 | Reforming fuel to hydrogen, employs electrically-heated composite membrane incorporating catalytic metallic layer separating hydrogen from reactor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2002092500A1 true WO2002092500A1 (en) | 2002-11-21 |
Family
ID=7684392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2002/004910 WO2002092500A1 (en) | 2001-05-11 | 2002-05-04 | Catalytically active separating membrane for producing high-purity hydrogen |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE10122888A1 (en) |
| WO (1) | WO2002092500A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004019263B4 (en) * | 2003-04-29 | 2009-11-26 | Presting, Hartmut, Dr.Rer.Nat. | Apparatus for producing near-pure hydrogen by reforming and method of manufacturing the apparatus |
| US7648566B2 (en) | 2006-11-09 | 2010-01-19 | General Electric Company | Methods and apparatus for carbon dioxide removal from a fluid stream |
| US7966829B2 (en) | 2006-12-11 | 2011-06-28 | General Electric Company | Method and system for reducing CO2 emissions in a combustion stream |
| US8597383B2 (en) | 2011-04-11 | 2013-12-03 | Saudi Arabian Oil Company | Metal supported silica based catalytic membrane reactor assembly |
| US9745191B2 (en) | 2011-04-11 | 2017-08-29 | Saudi Arabian Oil Company | Auto thermal reforming (ATR) catalytic structures |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010010822A1 (en) * | 2010-03-10 | 2011-09-15 | Eads Deutschland Gmbh | Device, useful for producing hydrogen gas by dehydrogenating hydrocarbon fuel, comprises fuel reservoir connected with reactor via fuel supplying line to supply fuel from reservoir into reactor, and heating device for heating supplied fuel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004019263B4 (en) * | 2003-04-29 | 2009-11-26 | Presting, Hartmut, Dr.Rer.Nat. | Apparatus for producing near-pure hydrogen by reforming and method of manufacturing the apparatus |
| US7648566B2 (en) | 2006-11-09 | 2010-01-19 | General Electric Company | Methods and apparatus for carbon dioxide removal from a fluid stream |
| US7966829B2 (en) | 2006-12-11 | 2011-06-28 | General Electric Company | Method and system for reducing CO2 emissions in a combustion stream |
| US8597383B2 (en) | 2011-04-11 | 2013-12-03 | Saudi Arabian Oil Company | Metal supported silica based catalytic membrane reactor assembly |
| US9745191B2 (en) | 2011-04-11 | 2017-08-29 | Saudi Arabian Oil Company | Auto thermal reforming (ATR) catalytic structures |
| US10071909B2 (en) | 2011-04-11 | 2018-09-11 | Saudi Arabian Oil Company | Auto thermal reforming (ATR) catalytic structures |
| US10093542B2 (en) | 2011-04-11 | 2018-10-09 | Saudi Arabian Oil Company | Auto thermal reforming (ATR) catalytic structures |
| US10252911B2 (en) | 2011-04-11 | 2019-04-09 | Saudi Arabian Oil Company | Auto thermal reforming (ATR) catalytic systems |
| US10252910B2 (en) | 2011-04-11 | 2019-04-09 | Saudi Arabian Oil Company | Auto thermal reforming (ATR) catalytic structures |
Also Published As
| Publication number | Publication date |
|---|---|
| DE10122888A1 (en) | 2002-11-21 |
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