TW575467B - Catalytic reactor - Google Patents
Catalytic reactor Download PDFInfo
- Publication number
- TW575467B TW575467B TW91121313A TW91121313A TW575467B TW 575467 B TW575467 B TW 575467B TW 91121313 A TW91121313 A TW 91121313A TW 91121313 A TW91121313 A TW 91121313A TW 575467 B TW575467 B TW 575467B
- Authority
- TW
- Taiwan
- Prior art keywords
- catalytic reactor
- flow channel
- catalyst
- patent application
- reactor
- Prior art date
Links
- 230000003197 catalytic effect Effects 0.000 title claims description 31
- 239000003054 catalyst Substances 0.000 claims description 64
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000011888 foil Substances 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 18
- 238000002485 combustion reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000005215 recombination Methods 0.000 claims description 11
- 230000006798 recombination Effects 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000005524 ceramic coating Methods 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000004891 communication Methods 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 description 41
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 239000000919 ceramic Substances 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005485 electric heating Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000007084 catalytic combustion reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- MHCVCKDNQYMGEX-UHFFFAOYSA-N 1,1'-biphenyl;phenoxybenzene Chemical compound C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1OC1=CC=CC=C1 MHCVCKDNQYMGEX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- VLWBWEUXNYUQKJ-UHFFFAOYSA-N cobalt ruthenium Chemical compound [Co].[Ru] VLWBWEUXNYUQKJ-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- CKSRCDNUMJATGA-UHFFFAOYSA-N germanium platinum Chemical compound [Ge].[Pt] CKSRCDNUMJATGA-UHFFFAOYSA-N 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/34—Apparatus, reactors
- C10G2/341—Apparatus, reactors with stationary catalyst bed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/248—Reactors comprising multiple separated flow channels
- B01J19/249—Plate-type reactors
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- 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
- C01B3/384—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 the catalyst being continuously externally heated
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D9/00—Heat-exchange apparatus having stationary plate-like or laminated conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
- F28D9/0031—Heat-exchange apparatus having stationary plate-like or laminated conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits for one heat-exchange medium being formed by paired plates touching each other
- F28D9/0037—Heat-exchange apparatus having stationary plate-like or laminated conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits for one heat-exchange medium being formed by paired plates touching each other the conduits for the other heat-exchange medium also being formed by paired plates touching each other
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D9/00—Heat-exchange apparatus having stationary plate-like or laminated conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
- F28D9/0093—Multi-circuit heat-exchangers, e.g. integrating different heat exchange sections in the same unit or heat-exchangers for more than two fluids
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F3/00—Plate-like or laminated elements; Assemblies of plate-like or laminated elements
- F28F3/02—Elements or assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with recesses, with corrugations
- F28F3/04—Elements or assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with recesses, with corrugations the means being integral with the element
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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
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2451—Geometry of the reactor
- B01J2219/2453—Plates arranged in parallel
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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
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2461—Heat exchange aspects
- B01J2219/2465—Two reactions in indirect heat exchange with each other
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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
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2469—Feeding means
- B01J2219/247—Feeding means for the reactants
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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
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- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2469—Feeding means
- B01J2219/2471—Feeding means for the catalyst
- B01J2219/2472—Feeding means for the catalyst the catalyst being exchangeable on inserts other than plates, e.g. in bags
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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
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2476—Construction materials
- B01J2219/2477—Construction materials of the catalysts
- B01J2219/2479—Catalysts coated on the surface of plates or inserts
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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
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2476—Construction materials
- B01J2219/2483—Construction materials of the plates
- B01J2219/2485—Metals or alloys
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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
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2491—Other constructional details
- B01J2219/2497—Size aspects, i.e. concrete sizes are being mentioned in the classified document
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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
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2491—Other constructional details
- B01J2219/2498—Additional structures inserted in the channels, e.g. plates, catalyst holding meshes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Description
575467 五、發明說明(1 ) 本發明係關於適合使用於進行氣相反應之催化反應器 ’特別但非僅限用以進行高度放熱和吸熱反應,同時亦 關於使用該催化反應器之化學程序。 使用受載於金屬基體上之催化物質係眾所周知。舉例 而言,英國專利GB 1 490 977號中記述包含帶有鋁之鐵 素合金基體,且使用一層耐火氧化物例如氧化鋁、氧化 鈦或氧化锆,然後再用一種催化之鉑族金屬所塗覆於其 上之觸媒。如英國專利GB 1 5 3 1 1 34和1 564 097中所 述,一種觸媒本體可包括大體上平板片和交錯排列此物 質的波紋板,其係將數個此種板排列成爲堆疊或將兩個 此種板捲繞在一起成爲盤管之方式以界定通過該本體之 通道。此等實例中,平板和波紋板兩者具有經疊加在其 上之小尺寸波紋度來協助塗層之成形。此等觸媒本體亦 被掲示係適合使用於處理來自車輛之廢氣。關於這一點 ,因爲所有通道均流動相同之壓力及相同之氣體,一個 通道至其接鄰通道之熱傳並非是須要考慮的問題。歐洲 專利案EP 0 8 8 5 6 5 3 A ( Friedrich等所有)中記述一種 用於催化反應之密集型熱交換器,其中流通通道係由經 摺疊成爲六角形之單長薄片的金屬所界定,具位於摺疊 六角形的連續板間之波紋狀箔片;此波紋狀箔承載著觸 媒載體並加強各通道間之熱傳效應,在一個具體實施例 中,板一邊之氣體歷經放熱反應而板的另一邊者則歷經 吸熱反應。 根據本發明所提供之一種催化反應器,其包括經排列
575467 五、發明說明(3) 質構成)可經由縱向滑動方式由流通通道之開口端而取 出。 爲了保證所需要之良好熱接觸,第一和第二流通通道 兩者在垂直於板之方向宜小於8毫米深度。更佳地第一 和第二流通通道兩者在該方向是小於5毫米深度(如果 此等通道係由只一片板中之溝槽所界定,然後此等相當 於溝槽之深度)。爲使各板能耐不同流通通道間之流體 之鉅大壓差。各通道在與板成切線之方向宜不超過50 毫米寬。 各板宜是平直,具有經機器或蝕刻所成橫越其表面之 溝槽以界定流通通道。該反應器可因此包含一疊平板, 其具有足夠厚度以承受必要壓差,且循不同路徑(其亦 提供結構完整性)的鄰接板上之溝槽。舉例而言,溝槽 可能是20毫米寬,此寬度係由至其曝露的板之壓力差 予以決定的,每一溝槽寬度適應使用觸媒物質所塗覆之 材料的一或數片波紋狀箔。連結各板成爲一個整體結構 以保證流體通道的氣密性。 第一流通通道與對面上之第二流通通道宜呈鏡像之流 動路徑。如果接鄰之第一流通通道和第二流通通道係呈 傾斜方向,可突現此種路徑。在一個實例中,此堆疊具 有六角形狀及延伸在呈相對的一對板面間之每一流通管 道或者在另一具體實施例中,每板(而因此該堆疊)是 長方形,第一流通通道沿著板面長度的方向延伸,而第 二流體係循著相對集管間之至少兩個歪斜路徑流動。 575467 五、 發明說明 ( 5) 鐵 0 當 將 此 金 屬 在 空 氣 中 加 熱 時 它 形成 氧 化 鋁 的 氧 化 物 附 著 塗 層 其 保 護 該 合 金 免 於 進 一 步 之 氧 化 此 氧 化物 層 亦 保 護 該 合 金 在 甲 院 氧 化 反 應 器 或 水 蒸 汽 /甲 i烷重組反 應 器 中 普 遍 之 狀 況 下 免 於 腐 蝕 0 於使 用 此 金 屬 作 爲 觸 媒 基 體 5 且 用 倂 合 觸 媒 物 質 在 其 中 之 陶 瓷 層 予 以 塗 覆 之 情 況 咸 信 ·· 金 屬 上 之 氧 化 隹呂 氧 化 物 層 與 陶 瓷 塗 層 連 合 以 便保 證 ·· 觸 媒 物 質 黏 附 至 金 屬 基 髀 上 0 使 用 任 何 催 化 反 應 器 之 一 個 難 題 爲 觸 媒 可 能 減 少活性 而 因 此 必 須 更 換 〇 因 爲 設 計 此 等 反 應 器 係 適 合在 高 溫 和 壓 力 下 使 用 各 板 係依某 一 種 程 序 而 予 以 連 結 在 —* 起 例 如 擴 散 黏 結 ( 其保 證 爲 氣 密 式 密 封 ) > 但 是 可 能 需 要 能 再 利 用 此 整 體 之 結 構 同 時 能 更 換 觸 媒 〇 再 者 可 能 需 要 兩 種 氣 流 之 同 向 或 逆 向 流 動 , 而 非 橫 向 流 動 以 獲 得 令 人 滿 意 之 溫 度 分 佈 > 兩 種 流 通 通 道 的 傾 斜 流 動 方 向 即 類 似 於此 〇 爲 了 某 些 的 觸 媒 金 屬 可 能 不 直 接 沈 積 在 金 屬 的 黏 附 之 氧 化 物 塗 層 上 ( 4nc 任何 陶 瓷 層 ) 0 特 別 如 果 欲 使 用 此 反 應 器 於 吸 熱 反 應 > 可 能 需 要 經 由 直 接 之 電 加 熱 來 昇 局 反 應 器 之 溫 度 至 所 需 要 之 操 作 溫 度 將 電 流 通 經 形 成 反 應 器 之 各 板 〇 —^ 般 此 可 能 僅 在 起 始 而 爲 之 5 隨 後 1 熱 係 由 第 二 氣 體 流 通 通 道 中 所 進 行 之 放 熱 反 應 而 提 供 或 經 由 熱 氣 體 ( 舉 例 而 5 來 白 內 燃 程 序 例 如 層 流 燃 燒 器 之 排 氣 ) 而 提 供 0 圖 式 簡 單 說 明 7-
575467 五、 發明說明 (6) 本 發 明 現 在將僅經由實例並參照附隨之圖式予以更進 —* 步 和 更 特 別敘述,圖式中: 第 1 圖 顯 示反應器的截面圖; 第 2 圖 顯 示另種催化反應器之截面圖。 可 將 本 發 明之反應器使用於轉化甲烷成爲較長鏈烴類 之 化 學 程 序 中。第一階段包括水蒸汽/甲烷重組,即:下 列 反 應 : 水蒸汽+甲院—一氧化碳+氫氣 此 反 應 是 吸熱性,並可能經由第一氣體流通通道中之 鉑 /铑觸媒予以催化。造成此反應所需要之熱可由燃燒甲 院 而 提 供 y 即:下列反應: 甲烷+氧-二氧化碳+水 其 是 放 熱 反 應,並可能經由接鄰之第二氣體流通通道中 之 鉑 /鈀觸媒予以催化。兩種此等反應可在大氣壓下進行 唯 兩 者 之 一,重組反應可在昇高之壓力下進行。可將 經 由 燃 燒 反 應所產生之熱傳導通過分隔接鄰通道之金屬 板 〇 經 由 水 蒸 汽/甲烷重組所產生之氣體混合物稱爲合成氣 〇 氫 其 本 身 可能是一種所需要之產物,例如供使用於燃 料 電 池 中 〇 或者,可使用實行Fischer-Tropsch合成之該 氣 體 混 合 物 ,即: — 氧 化 碳 +氫—鏈烷或烯烴(例如C1G) +水 此 反 應 是 放 熱反應,其在昇高之溫度(一般在200 °C至 3 5 0°C 間) 例如280°C及昇高之壓力(一般在2MPa至 -8-
575467 五、發明說明(7) 4MPa間)例如2.5MPa下,於觸媒例如鐵、鈷或熔化之 磁鐵礦存在下,並具有鉀、銶、铑或釔促進劑時發生。 經由該反應所形成之有機化合物的確實性質係基於溫度 和觸媒以及一氧化碳:氫氣之比率。經由此合成反應所 放出之熱可使用以提供水蒸汽/甲烷重組反應所需要之至 少部份的熱,舉例而言可使用一種熱傳流體例如氨或道 熱A(D〇wtherm A)或西熱(syltherm)(道化學公司之商標名) 以傳送來自Fischer-Tropsch合成正發生在其中之反應器之 熱’使用該熱來預熱經供應至重組反應器之至少一種氣流。 舉例而言,在重組步驟,將主要由甲烷連同小百分率 (例如1 〇% )的乙烷和丙烷所組成之進料氣體加熱至大 約400 °C,與亦在大約400 °C之水蒸汽氣流混合,然後 供應至催化反應器。兩種氣流可能在大氣壓力下,或舉 例而言,在高於大氣壓比如說lOOKPa之壓力下。其流 動宜是如此使水蒸汽:甲烷莫耳比在1 :1與2 :1間。反 應器的第一部份是具有400 °C之鎳甲烷化觸媒之預重組 器,其中,高碳數烷烴與水蒸汽反應而形成甲烷(和一 氧化碳)·,如果進料氣體實質上不含高碳數烷烴,則不 需要此預重組器。反應器之第二部份是具有鉑/铑觸媒之 重組器,其中甲烷與水蒸汽反應而形成一氧化碳和氫氣 。此反應可在85 (TC下實施。吸熱反應所需之熱可由在 接鄰氣流通道內之鈀或鉛觸媒上燃燒甲烷(及/或氫)而 提供,或者,來自外燃單元例如層流燃燒器之排氣,來 自燃燒器之氣體以逆向流動至通過重組器之氣流;此方 575467 五、發明說明(8) 式可使重組器中之反應氣體能達到高達1000°c之最後溫 度。於使用催化燃燒之情況,觸媒可倂合六鋁酸金屬鹽 (例如六鋁酸鎂)作爲基體,但是較佳之觸媒是r (伽馬) 氧化鋁上之鉑和鈀(1 〇重量%)。可將甲烷/氧氣混合物 沿著反應器分階段供應以保證其燃燒發生遍及其反應器 長度。 可使用自重組器出口之一氧化碳及氫氣的熱混合物來 提供熱至水蒸汽及至進料氣體。然後可將它更進一步處 理,舉例而言,予以壓縮並供應至催化反應器,彼等在 其中反應,歷經Fischer-Tropsch合成而形成鏈院經或相 似化合物。此等程序的總結果是:將甲烷轉化成爲較高 分子量烴類,在周圍溫度下其一般係液體。因此,可將 所需要之烴類經由冷卻與其餘之氣體分離,以便液體冷 凝。可將此等程序使用在油井或氣井中來轉化甲烷氣體 成爲液態烴其較易輸送。 現在述及第1圖,反應器1 〇 (舉例而言,適合於水蒸 汽/甲烷重組)包括一堆疊的板12,每一者係Fecr alloy 鋼,邊長250毫米和厚3毫米之每一六角形。將寬度20 毫米和深度2.5毫米的溝槽14機製入每一板中,自一邊 至相對近延伸越過每一板1 2,並經由3毫米寬度之台階 1 5予以分隔(爲了簡化,僅將四個此類溝槽1 4和三個 此等台階1 5顯示於圖中)。可將使用含有觸媒物質之 陶瓷塗層所塗覆之50微米厚Fecr alloy鋼並具有2.5毫米 高之波紋度之載體箔16滑動入每一溝槽14中(圖中僅 -10- 575467 五、發明說明(9) 顯示一個)。組合此等板1 2的堆疊,連續板1 2中溝槽 14的定向相差約60°,並使用Fecraii〇y鋼的平頂板蓋 覆;然後將該堆疊擴散結合在一起。然後嵌入波紋狀箔 1 6。然後將集管1 8附著至經組合之堆疊的面上。因此 ,氣體流通通道經由溝槽1 4予以界定;而各板1 2的方 向是致使:高於和低於任何一個板1 2,各板1 2中之流 動方向相互是在120° (此等溝槽係各自由虛線和鏈點 線予以指示)。 將水蒸汽/甲烷混合物供應至集管18a,而所產生之氫 氣和一氧化碳之混合物係通過集管1 8d現出。將甲烷/空 氣混合物供應通過集管1 8 c和1 8 e (即:集管1 8 d之任 一邊上之集管),以便來自燃燒程序之排氣通過集管 1 8b和1 8f而出現。因此,氣體流動是至少呈部份逆流 以便燃燒通道中最熱之區域(其接近那些通道之入口) 最接近於水蒸汽/甲烷重組反應之出口。 每一集管1 8包括環繞其周圍予以密封至堆疊外部之 簡單長方形蓋,以便掩蓋該堆疊之一個面。可將彼等焊 接在該堆疊之外部。或者,如果在昇高之壓力下兩者都 無氣體流動,則可將集管膛室1 8適度地夾持至堆疊之 外部在任一情況中,應了解:在於使用一段時期後,如 果任一或兩通道中之觸媒變成廢料,則可將集管1 8取 出或切斷,並移出相對應之負載觸媒之箔1 6而更換。 然後將集管1 8重新連接。 應了解:在堆疊之連續板1 2中,沈積在氣體流通通 -11- 575467 五、發明說明(1〇) 道中呈波紋狀箔1 6上之陶瓷的形式可能不同以及:觸 媒材質亦可能不同。舉例而言,陶瓷可能包含在氣體流 通通道其中之一之氧化鋁,在另一氣體流通通道中爲氧 化锆。自板1 2所形成之反應器1 0亦可能適合於進行 Fischer-Tropsch合成反應。因爲板12所形成之堆疊係 連合在一起。所以氣體流通通道是氣密(除去在每一終 端上與集管1 8相通以外),而板1 2和溝槽1 4的尺寸 是致使:輪替之氣體流通通道中之壓力可能大爲不同。 再者,波紋狀箔1 6的間距或排列方式沿著反應器通道 1 4之變更以便可調整催化活性而因此提供在反應器1〇 中之不同點上溫度或反應速率之控制。亦可將波紋狀箔 1 6成形,例如具有穿孔而促進通道1 4內流體之混合。 再者,部份的范1 6上可能並無觸媒。在每一情況中, 波紋度宜平行於氣體流動方向而延伸。 在反應器10之修正中,箔16再度爲Fecralloy材料但 是將觸媒材質係直接沈積至Fecralloy的氧化物層上。 現在述及第2圖,另一種反應器20包含Fecralloy鋼 板21的堆疊,每一板通常是長方形,450毫米長和150 毫米寬及3毫米厚。 在每一此種板2 1的上表面是由台階23所分隔的2毫 米深度之長方形溝槽22 (圖中顯示八個此種溝槽),但 是有溝槽22之三種不同排列。該圖式中所示之板2 1中 ,各溝槽22以相對於板21的縱軸線成45°之對角線延 伸,自頂部左側至底部右側如所示。第二型的板2 1中 -12- 575467 五、發明說明(12) 而所產生之氫氣和一氧化碳混合物係通過另一端上之集 管2 8而出現。將甲烷/空氣混合物供應至另一端上之兩 集管2 6的各室(如所示之左手端)而因此’來自燃燒 程序之排氣通過如所示右手端上之兩集管26的各室。 經供應至頂部左側集管室(如所示)之混合物的流動路 徑是通過對角線溝槽2 2而進入底部中側之集管室中’ 然後流動通過該堆疊的其他板中之對角線溝槽22a而入 頂部右側集管室中。因此,氣體流動是至少呈近似逆流 ,以使燃燒通道中之最熱區域(其係接近那些通道之入 口)最接近於水蒸氣/甲烷重組反應之出口。 在使用另種模式中,縱向溝槽22b中之氣體流動是呈 相反方向,因此,流動是至少近似呈同向流動。在任一 情況中,具有縱向溝槽22b之板的任一面上流動路徑是 在鏡像對角線方向’其提供較佳溫度分佈之好處以避免 熱點。 當必須更換觸媒時,此可能經由切除集管2 6與2 8 ’ 然後取出自經由溝槽22所界定之所有通道中之箔24並 更換箔2 4。集管2 6與2 8可再度聯結,此種流動佈置的 另外好處爲:亦可將燃燒用之燃料沿著反應器2〇之長 度供應至集管26的各室,此方式可能維持更均勻之燃 料/氧混合物。 形成堆疊之各板可能具有不同尺寸和形狀,而溝槽22 和22A可具有不同方向。舉例而言,各板之大小可能是 8〇〇毫米乘400毫米而溝槽係與縱向軸線成大約56° ( -14- 575467 五、發明說明(13 ) 如果有三個集管室沿著每一面)、成大約63° (如果有 四個集管室)或成大約68° (如果有五個集管室)。 在另外替代形式中,恰好有兩種型式之板,係具有縱 向溝槽2 2 b之板與具有橫向溝槽之板輪替,並將兩集管 26中之擋板27所交錯,一面上之擋板27係相對另一面 上連續擋板27間中途之各位置。因此,擋板27保證近 似逆流(或同向流動)之流動,唯彼等並不提供具有高於 和低於每一縱向溝槽板之鏡像對角線流動路徑之好處。 在使用之另種模式中,燃燒係在外部燃燒器中(例如 層流燃燒器)發生,大約900°或1 000°C之極熱排氣通 過反應器1〇或20的流通通道,將通過它之甲烷/空氣混 合物如下述之成爲與甲烷/水蒸汽流動呈逆流之流動。在 此情況中,不須提供箔在此具有陶瓷塗層或觸媒之那些 通道中,但是經由傳遞熱至分開之板1 2或2 1箔可加強 攜帶熱排氣之第二氣體流通通道與預重組器和重組器通 道中反應物間之熱傳。 在另外之修正中,能耐受流通通道間之壓力差之各板 ,例如反應器1〇中之板12或反應器20中之板21係由 能耐高溫和壓力之一種金屬所造成例如鈦或Inc alloy 8 0 0ΗΤ且可將它容易擴散結合。而如果需要陶瓷塗層( 作爲觸媒基體),該箔例如16和24可能由Fecralloy 鋼所造成。 在催化反應器的燃燒通道1 4中,如果使用催化燃燒來 產生熱(如所示),則可將燃燒觸媒本身使用薄多孔惰 -15- 575467 五、發明說明(14 ) 性陶瓷層蓋覆,以便限制氣體混合物與觸媒接觸而因此 限制反應速率特別在通道之開始處。 如較早所述,在供應氣體前,起始可使用電加熱,即 :將電流直接通經形成反應器之各板來昇高催化反應器 之溫度至例如400 °C,以保證發生催化燃燒。在操作期 間亦可使用此項電熱來調整反應器溫度。亦可使用電加 熱在反應器出口之附近以保證:例如9 0 0 °C之溫度經由 氣體歷經重組反應而達到。 在對於第2圖之反應器的修正中,板2 1是3 . 5毫米厚 而流通通道22是3毫米深和40毫米寬。使用由兩層之 波紋狀Fecralloy合金箔所組成之箔組合代替單箔24, 每一層具有50微米之厚度及經由平箔所分隔之廣闊1.4 毫米。將此等箔點焊接在一起,該組合係充分的長而延 伸相對應溝槽22之全長(唯另外,可能有兩個此類組 合,終端接終端放置在溝槽22中)。 在點焊此組合後,可能使它歷經900 °C之氧化處理。 然後將具有50至200米平方/克範圍內之表面面積的伽 馬氧化鋁含水漿體或溶膠(大約2 0 0克/升)經由噴射( 或浸漬)施加至該組合之表面上並乾燥。可重複此順序 數次而獲得50至3 00微米範圍內氧化鋁之厚度。然後 將氧化鋁煅燒。然後將鉑鍺鹽類混合物的稀水溶液經由 噴射和乾燥而施加,重複直至獲得所需要之金屬鹽的重 量負載。然後將該鹽還原而產生精細分散之觸媒金屬在 氧化鋁塗層上。(或者,可將氧化鋁分散入觸媒金屬鹽的 -16- 575467 五、發明說明(15) 溶液中,因此,將兩組份塗覆在一起)。然後可將攜帶 觸媒之組合嵌入流通通道22中。典型之金屬負載係在 5%至25%(wt)之範圍內,宜大約1〇%。 作爲觸媒受質之此種箔組合提供良好金屬對金屬接觸 而促進熱傳至或自通道之壁。熱和質傳之良好狀況亦發 生在該箔組合以內,因爲反應氣體至觸媒表面之路徑長 度一般是小於1毫米。在水蒸汽重組反應之情況中,反 應之動力學本來是快速而當反應是強烈吸熱時,動力學 時常受熱傳所限制。因此使用此種觸媒箔組合能容許反 應在小於50毫秒之滯留時間,以高轉化效率(>95%)進 行。 將使用於燃燒通道中之觸媒箔組合並以與上述者之相 以方式處理,唯較佳之觸媒是鈀或鉑與鈀之混合物。觸 媒之金屬受質容許燃燒觸媒以更均勻溫度分佈發揮功能 ,並消除觸媒表面上之熱點。因此,該觸媒可在900°C 下操作而不會使活性隨著時間顯著退化。經氧化之金屬 的富含氧化鋁之表面與陶瓷塗層形成重要之整體連合° 催化反應器20亦可能適合於進行Fischer-Tropsch合 成反應。在此情況中,該F i s c h e r - T r 〇 p s c h反應一般可能 在對角線流通通道22和22a中進行,同時可使冷卻劑 通經縱向通道22b。關於Fischer-Tropsch反應,必須將 觸媒比表面積(每單位體積的通道之表面面積)達_ ® 大以保證單程轉化通過反應器時及在一般可能在1 # 範圍內之經濟滯留時間,一氧化碳的大槪90%轉化率。 -17- 575467 五、發明說明(16 ) 舉例而言,需要4000至6000米平方/米立方範圍內之比 長面積。爲了此目的,每一對角線流通通道22和22a 可能需要4毫米深和20毫米寬且一般在0.1至1.0米長 的範圍內。在此情況中,因此,箔組合可能由比如5層 的波紋狀箔(具有0.7 5毫米廣闊)連同交插之4片平箔 所組成,且如上所述,在使用陶瓷和觸媒塗覆前,可將 此組合點焊在一起。 舉例而言,如上述,可將箔組合氧化,並以上述之方 式使用氧化鈦塗覆具有60至300米平方/克範圍內之比 表面積以便在燒結後獲得50至200微米厚之塗層。適 合此反應之適當觸媒可能是鈷(比如12%至40%)連同 小比例的促進劑例如釕(〇· 1至1 .〇% ),此等數字係催 化塗層(即:陶瓷加觸媒金屬)的重量百分率。其他促 進劑包括鍊、鈀或鉑、或氧化銷、氧化鑭或氧化钍。舉 例而言,可將混合之鈷釕鹽的水溶液重複施加至煅燒之 陶瓷並予乾燥,然後還原而獲得所需要之金屬負載。 應了解:因爲將觸媒金屬沈積在金屬受質上之薄陶瓷 塗層以內(比如1 〇〇微米厚),所以觸媒金屬必須在該 表面的那個距離以內而因此,經由反應物容易能接近。 (呈對比,關於固體陶瓷基質,觸媒鹽類可能擴散更遠 深入陶瓷中)。因爲化學反應產生液體產物,此液體會 將佔據陶瓷層中之孔隙;此液體限制經由擴散至催化部 位,氣體之接近,因此如果陶瓷層係超過比如300微米 厚,則可能有較大之趨勢而產生甲烷(而非較佳之長鏈
-18- 575467 五、發明說明(17 ) 烴類),因爲氫氣較一氧化碳擴散較快。金屬箔基質的 另外優點是協助移除可能易於造成熱點之反應熱。此亦 減少甲烷之形成,因爲甲烷形成易於隨著溫度而增加。 亦致使觸媒甚少易受由於結焦而變成失去活性。 液相之存在於觸媒表面上亦減少反應器的總產率。如 果,依上文所述,將Fischer-Tropsch合成在對角線通道 22和22a中實施,則在連接各通道之集管26中,可將 液相和汽相分開。此現象可經由提供一個除霧組件在較 接近出口之集管26的各室中而加強。然後可將液體產 物自此等室之基底排放出。在每一通道以內,氣體係平 行於波紋度而流動,以致液體易於被夾帶,將液體積聚 在觸媒表面上之情形減至最少。 對角線通道22、22a之大小亦可沿著反應器20之長 度而變更,如亦可能變更帶有觸媒之箔組合的形狀。舉 例而言,較接近反應器出口端之通道可能較窄,以便增 加通道中之線速度。 觸媒層可含有除去金屬箔以外之物質。特別,自使用 經燒結之Fecralloy纖維的薄片,舉例而言例如自 Microfiltrex公司可供應者可能有益。此薄片中,纖維 具有大約5至1 0微米之直徑,該結構係充分開敞以致 孔隙度在7〇至90%範圍內,而薄片係具有大約0.5毫米 之厚度。此種薄片可能是波紋狀或摺撊適合使用在流通 通道中。 如上述,可將此薄片氧化,然後浸沒入氧化鋁溶膠中 -19- 575467 五、發明說明(19) 10、20…反應器 12、21…堆疊的板 14、 22···溝槽 15、 23···台階 16、 24···載體箔片 18、26…集管(室) 27…鰭片 •21 -
Claims (1)
- 575467 ___ p告本__ 六、申請專利範圍 第9 1 1 2 1 3 1 3號「催化反應器」專利案 (9 1年1 2月修正) 六、申請專利範圍: 1· 一種催化反應器,包括經排列成堆疊並連合在一起 之複數金屬板’此_板在接鄰各板間界定第一流通 通道’交替地與具有與接鄰各板間之第二流通通道 以便保證流體在第一流通通道與第二流通通道中具 有良好之熱接觸,第二流通通道的流向與第一流通 通道之流向不同,在至少第二流通通道以內提供將 流體可滲透之’觸媒層,供應各自之流體至流通通道 之管集,每一個第一集管包含經銜接至該堆疊外部 之腔室並與複數第一流通通道相通,而每一個第二 集管包含經銜接至該堆疊外部之一個腔室並與複數 第二流通通道相通,以致於在移去一個集管後,相 對應的流通通道中之觸媒層即可拆卸。 2·如申請專利範圍第1項之催化反應器,其中觸媒層 包括具有觸媒塗層之流體可滲透之金屬熱傳層。 3. 如申請專利範圍第2項之催化反應器,其中該觸媒 塗層是包含觸媒之陶瓷塗層。 4. 如申請專利範圍第2項之催化反應器,其中該觸媒 層包含至少一具有觸媒的陶瓷塗層之波紋狀金屬箔 片。 5·如申請專利範圍第1項之催化反應器,其中接鄰 4»575467 六、申請專利範圍 之 第 一 和 第 二流通通道係呈傾斜交叉。 6.如 甲 請 專 利 範圍第5項之催化反應器, 其中 第 二 流 通 通 道 在 與 相對面上之第一流通通道係呈鏡像。 7·如 串 請 專 利 範圍第1項之催化反應器, 其中 堆 疊 中 之 每 — 板 係 呈有六邊形,每一流通通道 在對 側 之 成 對 的 板 面 間 延伸。 8.如 串 Ξ主 曰円 專 利 範圍第1項之催化反應器, 其中 堆 疊 中 之 每 一 板 面 是長方形,第一流通通道沿 著板 的 長 度 而 延 伸 而 第二流通通道係橫越各自之 板而 呈 傾 斜 延 伸 以 便 於 第二流通通道可循著相對之 集管 間 至 少 兩 個 傾 斜 路 徑。 9. 一 種 進 行 烴 類的水蒸汽重組之方法,其 中供 應 水 基 y \ \\ 汽 和 烴 類 的 混合物至如申請專利範圍第 1至 8 項 中 任 一 項 之 反 應器的第二流通通道,並提 供熱 源 至 第 一 流 通 通 道 〇 10.如 串 請 專 利 範圍第9項之方法,其中該 熱源 是 一 種 可 燃 之 氣 體 混合物,並將流體可滲透之 觸媒 層 提 供 在 第 一 流 通 通道內,摻合供燃燒用之一種觸媒。 11.— 種 處 理 甲 烷而產製較長鏈烴類之裝置 ,該 裝 置 包 括 第 —* 催 化 反應器用以進行水蒸汽/甲烷 之重 組 及 第 二 催 化 反 m hvu\ 器用以進行費-托(Fischer- T r op s C h) 之 合 成 每 — 催化反應器係如申請專利範圍第 1 至 8 項 任 項 中 之催化反應器;用以傳送第 -2- 一催 化 反 應575467 六、申請專利範圍 器之產物至第二催化反應器之設備’該傳送設備結 合至少一個熱交換器以便移除來自產物之熱,及至 少一個壓縮設備以便增加產物之壓力;以及冷凝自 費-托(Fi schei-Tfopsch)合成反應所產生之流體混 合物的液體組分之設備。
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- 2002-09-12 AU AU2002331937A patent/AU2002331937B2/en not_active Ceased
- 2002-09-12 WO PCT/GB2002/004144 patent/WO2003033131A1/en active IP Right Grant
- 2002-09-12 US US10/491,782 patent/US7201883B2/en not_active Expired - Fee Related
- 2002-09-12 EP EP02767635A patent/EP1434652B1/en not_active Expired - Lifetime
- 2002-09-12 DE DE60203018T patent/DE60203018T2/de not_active Expired - Fee Related
- 2002-09-12 BR BRPI0213170-6A patent/BR0213170B1/pt not_active IP Right Cessation
- 2002-09-18 TW TW91121313A patent/TW575467B/zh not_active IP Right Cessation
- 2002-09-19 MY MYPI20023483A patent/MY126177A/en unknown
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2004
- 2004-04-15 NO NO20041616A patent/NO330499B1/no not_active IP Right Cessation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI403364B (zh) * | 2005-01-31 | 2013-08-01 | Compactgtl Ltd | 催化反應器 |
Also Published As
Publication number | Publication date |
---|---|
DE60203018D1 (de) | 2005-03-24 |
US7201883B2 (en) | 2007-04-10 |
US20050013769A1 (en) | 2005-01-20 |
EP1434652B1 (en) | 2005-02-16 |
BR0213170A (pt) | 2004-09-14 |
NO330499B1 (no) | 2011-05-02 |
AU2002331937B2 (en) | 2007-07-05 |
EP1434652A1 (en) | 2004-07-07 |
DE60203018T2 (de) | 2005-07-07 |
BR0213170B1 (pt) | 2012-08-07 |
NO20041616L (no) | 2004-04-15 |
WO2003033131A1 (en) | 2003-04-24 |
MY126177A (en) | 2006-09-29 |
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