EP1109622A2 - Synthese de fischer-tropsch utilisant des catalyseurs sur des supports mesoporeux - Google Patents
Synthese de fischer-tropsch utilisant des catalyseurs sur des supports mesoporeuxInfo
- Publication number
- EP1109622A2 EP1109622A2 EP99943789A EP99943789A EP1109622A2 EP 1109622 A2 EP1109622 A2 EP 1109622A2 EP 99943789 A EP99943789 A EP 99943789A EP 99943789 A EP99943789 A EP 99943789A EP 1109622 A2 EP1109622 A2 EP 1109622A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- cobalt
- support
- group
- catalytically active
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 151
- 238000000034 method Methods 0.000 title claims abstract description 59
- 230000008569 process Effects 0.000 title claims abstract description 36
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 70
- 239000010941 cobalt Substances 0.000 claims abstract description 70
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052751 metal Inorganic materials 0.000 claims abstract description 58
- 239000002184 metal Substances 0.000 claims abstract description 58
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 42
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 41
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- 229910052702 rhenium Inorganic materials 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 16
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical group [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052762 osmium Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052706 scandium Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000010944 silver (metal) Substances 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 229910021012 Co2(CO)8 Inorganic materials 0.000 claims 1
- 150000001242 acetic acid derivatives Chemical class 0.000 claims 1
- 125000005595 acetylacetonate group Chemical group 0.000 claims 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt(II) nitrate Inorganic materials [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 229910001868 water Inorganic materials 0.000 description 23
- 239000007789 gas Substances 0.000 description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 22
- 239000007788 liquid Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 239000000499 gel Substances 0.000 description 16
- 150000002739 metals Chemical class 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
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- IBIKHMZPHNKTHM-RDTXWAMCSA-N merck compound 25 Chemical compound C1C[C@@H](C(O)=O)[C@H](O)CN1C(C1=C(F)C=CC=C11)=NN1C(=O)C1=C(Cl)C=CC=C1C1CC1 IBIKHMZPHNKTHM-RDTXWAMCSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000352 supercritical drying Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical class O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
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- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- VLWBWEUXNYUQKJ-UHFFFAOYSA-N cobalt ruthenium Chemical compound [Co].[Ru] VLWBWEUXNYUQKJ-UHFFFAOYSA-N 0.000 description 1
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- 230000009849 deactivation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
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- 230000002939 deleterious effect Effects 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000368 destabilizing effect Effects 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
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- 239000002574 poison Substances 0.000 description 1
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- 239000012256 powdered iron Substances 0.000 description 1
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- 230000000630 rising effect Effects 0.000 description 1
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- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
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- C07C1/043—Catalysts; their physical properties characterised by the composition
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- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
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- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
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- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
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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
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- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
Definitions
- the present invention relates to a process for the preparation of hydrocarbons from synthesis gas, (i.e., a mixture of carbon monoxide and hydrogen), typically labeled the Fischer-Tropsch process.
- synthesis gas i.e., a mixture of carbon monoxide and hydrogen
- this invention relates to supported catalysts containing metals on mesoporous materials.
- methane the main component of natural gas, are available in many areas of the world.
- Methane can be used as a starting material for the production of hydrocarbons.
- the conversion of methane to hydrocarbons is typically carried out in two steps. In the first step methane is reformed with water or partially oxidized with oxygen to produce carbon monoxide and hydrogen
- syngas (i.e., synthesis gas or syngas).
- syngas is converted to hydrocarbons.
- the preparation of hydrocarbons from synthesis gas is well known in the art and is usually referred to as Fischer-Tropsch synthesis, the Fischer-Tropsch process, or Fischer-Tropsch reaction(s).
- Catalysts for use in such synthesis usually contain a catalytically active Group VIII (CAS) metal.
- CAS catalytically active Group VIII
- iron, cobalt, nickel, and ruthenium have been abundantly used as the catalytically active metals.
- Cobalt and ruthenium have been found to be most suitable for catalyzing a process in which synthesis gas is converted to primarily hydrocarbons having five or more carbon atoms (i.e., where the C5 + selectivity of the catalyst is high).
- the catalysts often contain one or more promoters and a support or carrier material.
- Rhenium is a widely used promoter.
- the Fischer-Tropsch reaction involves the catalytic hydrogenation of carbon monoxide to produce a variety of products ranging from methane to higher aliphatic alcohols. The methanation reaction was first described in the early 1900's, and the later work by Fischer and Tropsch dealing with higher hydrocarbon synthesis was described in the 1920's.
- the Fischer-Tropsch synthesis reactions are highly exothermic and reaction vessels must be designed for adequate heat exchange capacity. Because the feed streams to Fischer-Tropsch reaction vessels are gases while the product streams include liquids, the reaction vessels must have the ability to continuously produce and remove the desired range of liquid hydrocarbon products.
- the process has been considered for the conversion of carbonaceous feedstock, e.g., coal or natural gas, to higher value liquid fuel or petrochemicals.
- the first major commercial use of the Fischer-Tropsch process was in Germany during the 1930's. More than 10,000 B/D (barrels per day) of products were manufactured with a cobalt based catalyst in a fixed-bed reactor. This work has been described by Fischer and Pichler in Ger. Pat. No. 731,295 issued Aug. 2, 1936.
- Catalyst supports for catalysts used in Fischer-Tropsch synthesis of hydrocarbons have typically been oxides (e.g., silica, alumina, titania, zirconia or mixtures thereof, such as silica- alumina). It has been claimed that the Fischer-Tropsch synthesis reaction is only weakly dependent on the chemical identity of the metal oxide support (see E. Iglesia et al. 1993, In: "Computer-Aided Design of Catalysts," ed. E. R. Becker et al., p. 215, New York, Marcel Dekker, Inc.). The products prepared by using these catalysts usually have a very wide range of molecular weights.
- oxides e.g., silica, alumina, titania, zirconia or mixtures thereof, such as silica- alumina.
- U.S. Pat. No. 4,477,595 discloses ruthenium on titania as a hydrocarbon synthesis catalyst for the production of C5 to C40 hydrocarbons, with a majority of paraffins in the C5 to C20 range.
- Pat. No. 4,542,122 discloses a cobalt or cobalt-thoria on titania having a preferred ratio of rutile to anatase, as a hydrocarbon synthesis catalyst.
- U.S. Pat. No. 4,088,671 discloses a cobalt-ruthenium catalyst where the support can be titania but preferably is alumina for economic reasons.
- U.S. Pat. No. 4,413,064 discloses an alumina supported catalyst having cobalt, ruthenium and a Group IILA or Group IVB metal oxide, e.g., thoria.
- European Patent No. 142,887 discloses a silica supported cobalt catalyst together with zirconium, titanium, ruthenium and/or chromium.
- U.S. Pat. No. 4,801,573 discloses a promoted cobalt and rhenium catalyst, preferably supported on alumina that is characterized by low acidity, high surface area, and high purity, which properties are said to be necessary for high activity, low deactivation, and high molecular weight products.
- the amount of cobalt is most preferably about 10 to 40 wt % of the catalyst.
- the content of rhenium is most preferably about 2 to 20 wt % of the cobalt content.
- Related U.S. Pat. No. 4,857,559 discloses a catalyst most preferably having 10 to 45 wt % cobalt and a rhenium content of about 2 to 20 wt % of the cobalt content.
- U.S. Pat. No. 5,545,674 discloses a cobalt-based catalyst wherein the active metal is dispersed as a very thin film on the surface of a particulate support, preferably silica or titania or a titania-containing support.
- the catalyst may be prepared by spray techniques.
- U.S. Pat. No. 5,028,634 discloses supported cobalt-based catalysts, preferably supported on high surface area aluminas.
- High surface area supports are said to be preferred because greater cobalt dispersion can be achieved as cobalt is added, with less tendency for one crystal of cobalt to fall on another crystal of cobalt.
- the cobalt loading on a titania support is preferably 10 to 25 wt %, while the preferred cobalt loading on an alumina support is 5 to 45 wt %.
- UK Patent Application GB 2,258,414A discloses a supported catalyst containing cobalt, molybdenum and/or tungsten, and an additional element.
- the support is preferably one or more oxides of the elements Si, Al, Ti, Zr, Sn, Zn, Mg, and elements with atomic numbers from 57 to 71.
- the preferred cobalt content is from 5 to 40 wt % of the catalyst.
- a preferred method of preparation of the catalyst includes the preparation of a gel containing the cobalt and other elements.
- a gel may be described as a coherent, rigid three-dimensional polymeric network.
- the present gels are formed in a liquid medium, usually water, alcohol, or a mixture thereof.
- the term "alcogel” describes gels in which the pores are filled with predominantly alcohol. Gels whose pores are filled primarily with water may be referred to as aquagels or hydrogels.
- a "xerogel” is a gel from which the liquid medium has been removed and replaced by a gas.
- the structure is compressed and the porosity reduced significantly by the surface tension forces that occur as the liquid is removed.
- surface tension creates concave menisci in the gel's pores.
- the menisci retreat into the gel body, compressive forces build up around its perimeter, and the perimeter contracts, drawing the gel body inward.
- surface tension causes significant collapse of the gel body and a reduction of volume, often as much as two- thirds or more of the original volume. This shrinkage causes a significant reduction in the porosity, often as much as 90 to 95 percent depending on the system and pore sizes.
- an "aerogel” is a gel from which the liquid has been removed in such a way as to prevent significant collapse or change in the structure as liquid is removed. This is typically accomplished by heating the liquid-filled gel in an autoclave while maintaining the prevailing pressure above the vapor pressure of the liquid until the critical temperature of the liquid has been exceeded, and then gradually releasing the vapor, usually by gradually reducing the pressure either incrementally or continuously, while maintaining the temperature above the critical temperature.
- the critical temperature is the temperature above which it is impossible to liquefy a gas, regardless of how much pressure is applied. At temperatures above the critical temperature, the distinction between liquid and gas phases disappears and so do the physical manifestations of the gas/liquid interface.
- Aerogels produced by supercritical drying typically have high porosities, on the order of from 50 to 99 percent by volume.
- This invention provides a process for producing hydrocarbons.
- the process comprises contacting a feed stream comprising hydrogen and carbon monoxide with a catalyst in a reaction zone maintained at conversion-promoting conditions effective to produce an effluent stream comprising hydrocarbons.
- the catalyst used in the process comprises (a) at least one catalytic metal for Fischer-Tropsch reactions (e.g., at least one metal selected from the group consisting of iron, cobalt, nickel and ruthenium); and (b) a non-layered mesoporous support which exhibits an X-ray diffraction after calcination that has at least one peak at a d-spacing of greater than 18 Angstrom units.
- the catalyst used in the process comprises a catalytically active metal selected from the group consisting of iron, cobalt, nickel, ruthenium, and combinations thereof, a support material comprising an inorganic, non-layered mesoporous crystalline phase with a composition represented by M n /q(W a X ⁇ ) Y c Z ( ⁇ Oj 1 ) where M is at least one ion selected from the group consisting of ammonium, sodium, potassium, and hydrogen, n is the charge of the composition excluding M expressed as oxides, q is the weighted molar average valence of M, n/q is the mole fraction of M, W is at least one divalent element, X is at least one trivalent element, Y is at least one tetravalent element, Z is at least one pentavalent, a, b, c, and d are mole fractions of W, X, Y and Z, respectively, h is a number from 1
- This invention also includes a Fischer-Tropsch catalyst comprising at least one catalytically active metal and a non-layered mesoporous support that exhibits an X-ray diffraction pattern after calcination that has at least one peak at a d-spacing of greater than 18 Angstrom units.
- This invention also includes a method for the preparation of a Fischer-Tropsch catalyst comprising impregnating a support with a salt of a catalytically active metal selected from the group consisting of iron, cobalt, nickel, ruthenium, and combinations thereof, wherein the support comprises a non-layered mesoporous support that exhibits an X-ray diffraction pattern after calcination that has at least one peak at a d-spacing of greater than 18 Angstrom units, and drying the impregnated support.
- the feed gases charged to the process of the invention comprise hydrogen, or a hydrogen source, and carbon monoxide.
- H 2 /CO mixtures suitable as a feedstock for conversion to hydrocarbons according to the process of this invention can be obtained from light hydrocarbons such as methane by means of steam reforming, partial oxidation, or other processes known in the art.
- the hydrogen is preferably provided by free hydrogen, although some Fischer-Tropsch catalysts have sufficient water gas shift activity to convert some water to hydrogen for use in the Fischer-Tropsch process. It is preferred that the molar ratio of hydrogen to carbon monoxide in the feed be greater than 0.5:1 (e.g., from about 0.67 to 2.5).
- the feed gas stream preferably contains hydrogen and carbon monoxide in a molar ratio of about 2:1.
- the feed gas stream preferably contains hydrogen and carbon monoxide in a molar ratio of about 0.67:1.
- the feed gas may also contain carbon dioxide.
- the feed gas stream should contain a low concentration of compounds or elements that have a deleterious effect on the catalyst, such as poisons.
- the feed gas may need to be pre-treated to ensure that it contains low concentrations of sulfur or nitrogen compounds, such as hydrogen sulfide, ammonia and carbonyl sulfides.
- the feed gas is contacted with the catalyst in a reaction zone.
- Mechanical arrangements of conventional design may be employed as the reaction zone including, for example, fixed bed, fluidized bed, slurry phase, slurry bubble column or ebullating bed reactors, among others, may be used. Accordingly, the size and physical form of the catalyst particles may vary depending on the reactor in which they are to be used.
- a component of the catalysts used in this invention is the support material (b) which carries the active catalyst component (a).
- the support material contains an inorganic, non-layered mesoporous crystalline phase with a composition of the formula: M n /q(W a Xj ) Y c Z ( jO n ) where M is one or more ions such as ammonium, sodium, potassium and/or hydrogen; n is the charge of the composition excluding M expressed as oxides; q is the weighted molar average valence of M; n/q is the number of moles or mole fraction of M; W is one or more divalent elements such as a divalent first row transition metal, (e.g., manganese, iron and cobalt) and/or magnesium, preferably cobalt; X is one or more trivalent elements such as aluminum, boron, iron and/or gallium, preferably aluminum; Y is one or more tetravalent elements (e.g., titanium, zir
- compositions where (a + b + c) is less than d and h is 2.5 and Z is niobium or tantalum e.g., Nb2 ⁇ 5 and Ta2U5.
- the silica-based mesoporous M415 molecular sieves are preferred in the preparation of the catalysts of the present invention. These include Si-MCM-41 and Al-MCM-41, where Si-MCM-41 refers to purely siliceous MCM-41 and Al-MCM-41 refers to MCM-41 where some Si atoms have been replaced by Al atoms.
- the catalytic metal is preferably selected from iron, cobalt, nickel and/or ruthenium. Normally, the metal component on the support is reduced to provide elemental metal (e.g., elemental iron, cobalt, nickel and/or ruthenium) before use.
- the catalyst contains a catalytically effective amount of the metal component(s). The amount of catalytic metal present in the catalyst may vary widely. Typically, the catalyst comprises about 1 to 50% by weight (as the metal) of total supported iron, cobalt, nickel and/or ruthenium per total weight of catalytic metal and support, preferably, about 1 to 30% by weight.
- Each of the metals can be used individually or in combination with other metals, especially cobalt and ruthenium, cobalt and rhenium, and cobalt and platinum.
- the catalyst may comprise one or more additional promoters or modifiers known to those skilled in the art.
- suitable promoters include at least one metal selected from the group consisting of Group IA (CAS) metals (i.e., Na, K, Rb, Cs), Group IIA metals (i.e., Mg, Ca, Sr, Ba), Group IB metals (i.e., Cu, Ag, and Au), Group IIIB metals (i.e., Sc, Y and La), Group IVB metals (i.e., Ti, Zr and Hf), Group VB metals (i.e., V, Nb and Ta), and Rh, Pd, Os, Ir, Pt, Mn, B, P, and Re.
- CAS Group IA
- CAS Group IA metals
- Group IIA metals i.e., Mg, Ca, Sr, Ba
- Group IB metals i.e., Cu, Ag, and Au
- Group IIIB metals i.e., Sc
- any additional promoters for the cobalt and/or ruthenium are selected from Sc, Y and La, Ti, Zr, Hf, Rh, Pd, Os, Ir, Pt, Re, Nb, Cu, Ag, Mn, B, P, and Ta.
- any additional promoters for the iron catalysts are selected from Na, K, Rb, Cs, Mg, Ca, Sr and Ba.
- the amount of additional promoter, if present, is typically between 0.001 and 40 parts by weight per 100 parts of the support or carrier. Combinations of cobalt and rhenium and combinations of cobalt and platinum are preferred.
- catalysts comprising from about 10 to 30% by weight of a combination of cobalt and rhenium, where the rhenium content is from about 0.001 to about 1 weight %; and catalysts comprising from about 10 to 30% of a combination of cobalt and platinum where the platinum content is from about 0.001 to 1 weight %.
- the catalysts of the present invention may be prepared by methods known to those skilled in the art. These include impregnating the catalytically active compounds or precursors onto a support, extruding one or more catalytically active compounds or precursors together with support material to prepare catalyst extrudates and spray-drying the supported catalytically active compounds. Accordingly, the supported catalysts of the present invention may be used in the form of powders, particles, pellets, monoliths, honeycombs, packed beds, foams, and aerogels.
- the most preferred method of preparation may vary among those skilled in the art, depending for example on the desired catalyst particle size. Those skilled in the art are able to select the most suitable method for a given set of requirements.
- a supported metal catalyst e.g., a supported cobalt catalyst
- a supported cobalt catalyst is by incipient wetness impregnation of the support with an aqueous solution of a soluble metal salt such as nitrate, acetate, acetylacetonate or the like.
- Another method involves preparing the catalyst from a molten metal salt.
- the support can be impregnated with a molten metal nitrate (e.g.,
- the support can be impregnated with a solution of zero valent cobalt such as C ⁇ 2(CO)g, C ⁇ 4(CO)i2 or the like in a suitable organic solvent (e.g., toluene).
- a suitable organic solvent e.g., toluene
- the impregnated support is dried and reduced with hydrogen.
- the hydrogen reduction step may not be necessary if the catalyst is prepared with zero valent cobalt.
- the impregnated support is dried, oxidized with air or oxygen and reduced with hydrogen.
- the metal(s) of the catalytic metal component (a) of the catalysts of the present invention is present in a reduced state (i.e., in the metallic state). Therefore, it is normally advantageous to activate the catalyst prior to use by a reduction treatment, in the presence of hydrogen at an elevated temperature.
- the catalyst is treated with hydrogen at a temperature in the range of from about 75°C to about 500°C, for about 0.5 to about 24 hours at a pressure of about 1 to about 75 atm. Pure hydrogen may be used in the reduction treatment, as well as a mixture of hydrogen and an inert gas such as nitrogen.
- the amount of hydrogen may range from about 1 % to about 100% by volume.
- the Fischer-Tropsch process is typically run in a continuous mode.
- the gas hourly space velocity through the reaction zone typically may range from about 100 volumes/hour/volume catalyst (v/hr/v) to about 10,000 v/hr/v, preferably from about 300 v/hr/v to about 2,000 v/hr/v.
- the reaction zone temperature is typically in the range from about 160°C to about 300°C.
- the reaction zone is operated at conversion promoting conditions at temperatures from about 190°C to about 260°C.
- the reaction zone pressure is typically in the range of about 80 psig (653 kPa) to about 1000 psig (6994 kPa), preferably, from 80 psig (653 kPa) to about 600 psig (4237 kPa), and still more preferably, from about 140 psig (1066 kPa) to about 400 psig (2858 kPa).
- the products resulting from the process will have a great range of molecular weights.
- the carbon number range of the product hydrocarbons will start at methane and continue to the limits observable by modern analysis, about 50 to 100 carbons per molecule.
- the process is particularly useful for making hydrocarbons having five or more carbon atoms, especially when the above-referenced preferred space velocity, temperature and pressure ranges are employed.
- the wide range of hydrocarbons produced in the reaction zone will typically afford liquid phase products at the reaction zone operating conditions. Therefore the effluent stream of the reaction zone will often be a mixed phase stream including liquid and vapor phase products.
- the effluent stream of the reaction zone may be cooled to effect the condensation of additional amounts of hydrocarbons and passed into a vapor-liquid separation zone separating the liquid and vapor phase products.
- the vapor phase material may be passed into a second stage of cooling for recovery of additional hydrocarbons.
- the liquid phase material from the initial vapor-liquid separation zone, together with any liquid from a subsequent separation zone, may be fed into a fractionation column.
- a stripping column is employed first to remove light hydrocarbons such as propane and butane.
- the remaining hydrocarbons may be passed into a fractionation column where they are separated by boiling point range into products such as naphtha, kerosene and fuel oils.
- Hydrocarbons recovered from the reaction zone and having a boiling point above that of the desired products may be passed into conventional processing equipment such as a hydrocracking zone in order to reduce their molecular weight.
- the gas phase recovered from the reactor zone effluent stream after hydrocarbon recovery may be partially recycled if it contains a sufficient quantity of hydrogen and/or carbon monoxide.
- Each of the catalyst samples was treated with hydrogen prior to use in the Fischer-Tropsch reaction.
- the catalyst sample was placed in a small quartz crucible in a chamber and purged with 500 seem (8.3 x 10 ⁇ 6 Vs) nitrogen at room temperature for 15 minutes.
- the sample was then heated under 100 seem (1.7 x 10" 6 m 3 /s) hydrogen at l°C/minute to 100°C and held at 100°C for one hour.
- the catalysts were then heated at l°C/minute to 400°C and held at 400°C for four hours under
- a 2 L pressure vessel was heated at 225°C under 1000 psig (6994 kPa) of H2:CO (2: 1) and maintained at that temperature and pressure for 1 hour.
- H2:CO 1: 1
- the reactor vessel was cooled in ice, vented, and an internal standard of di-n-butylether was added.
- the reaction product was analyzed on an HP6890 gas chromatograph. Hydrocarbons in the range of C11-C40 were analyzed relative to the internal standard. The lower hydrocarbons were not analyzed since they are masked by the solvent and are also vented as the pressure is reduced.
- a Cu + Productivity (g Cu + hour/kg catalyst) was calculated based on the integrated production of the C11-C40 hydrocarbons per kg of catalyst per hour.
- the solids were then calcined in air at the following according to the following schedule rates: from room temperature to 110°C at 10°C/min.; from 110°C to 200°C at 5°C/min.; and finally from 200°C to 550°C at l°C/min., where it was held for 4 hours before cooling to room temperature.
- An X-ray diffraction pattern of a sample of the recovered calcined solids showed it to have the MCM-41 structure with a peak at a d-spacing of 38 Angstroms.
- the Si-MCM-41 was used to prepare the catalyst described in Examples 1 to 9.
- Al-MCM-41 A thin suspension of AerosilTM 200 Si ⁇ 2 (10.1 g), H 2 0 (40 g) and tetramethylammoniumhydroxide (5.36 g, 25% in H2O) was prepared in a polyolefin bottle. The suspension was stirred for 20 minutes. To a solution of cetyltrimethylammoniumbromide (18.98 g), H2O (144.4 g) and a 50% in H2O NaOH solution (2.34 g) prepared by warming in a water-bath was added the Si ⁇ 2 suspension and stirred for 20 minutes. Aluminum isopropoxide (1.357 g) was added to the suspension and stirring was maintained for 12 minutes.
- the product was poured into a Teflon® (polytetrafluoroethylene) bottle; the bottle was sealed and put into an oven at 100°C for 3 days and 3 hours.
- the solids were filtered, washed with hot deionized water (3 L) and vacuum dried.
- the solids were then calcined in air at the following rates: from room temperature to 110°C at 10°C/min.; from 110°C to 200°C at 5°C/min.; and finally from 200°C to 550°C at l°C/min., where it was held for 4 hours before cooling to room temperature.
- the catalyst had a nominal composition of 5 wt. % Ru on Si-MCM-41.
- Si-MCM-41 (1.8 g) was slurried with an aqueous solution of RuCl (0.36 g) in a rotary evaporator. The water was removed under vacuum at 70°C. The dried material was calcined at 250°C under 1500 cc/minute of air.
- the catalyst had a nominal composition of 10 wt. % Ru/Si-MCM-41.
- Si-MCM-41 (2 g) was slurried with an aqueous solution of Co(N ⁇ 3)2-6H2 ⁇ (1.6 g) in a rotary evaporator. The water was removed under vacuum at 70°C. The dried material was calcined at 250°C under 1500 cc/minute of air. This material was slurried with an aqueous solution of
- Si-MCM-41 (2 g) was slurried with an aqueous solution of Pt(NH3)4(N ⁇ 3)2 (2.5 mg). The water was removed under vacuum at 70°C. This material was slurried with an aqueous solution of
- the catalyst had a nominal composition of 25 wt. % Co/0.05 wt. % Pt/Si-MCM-41.
- Si-MCM-41 (1.5 g) was slurried with an aqueous solution of Co(CH3COO)2-4H2 ⁇ (0.95 g) in a rotary evaporator. The water was removed under vacuum at 70°C. The dried material was calcined at 250°C under 1500 cc/minute of air.
- This material is designated Example 5A. A portion of this material (0.65 g) was slurried with an acetone solution of Co(CH3COO)2-4H2 ⁇ (0.4 g) and ruthenium acetylacetonate (3 mg, Ruacac3) in a rotary evaporator. The acetone was removed under vacuum at 70°C. The dried material was calcined at 250°C under 1500 cc/minute of air.
- the catalyst had a nominal composition of 25 wt. % Co/0.1 wt. % Ru/Si-MCM-41.
- Si-MCM-41 (1.5 g) was slurried with an aqueous solution of Co(N ⁇ 3)2-6H2 ⁇ (1.2 g) in a rotary evaporator. The water was removed under vacuum at 70°C. The dried material was calcined at 250°C under 1500 cc/minute of air. This material is designated Example 6B. A portion of this material (0.85 g) was slurried with an acetone solution of Co(N ⁇ 3)2-6H2 ⁇ (0.60 g) and Ruacac3
- the catalyst had a nominal composition of 25 wt. % Co/0.1 wt. % Ru/Si-MCM-41.
- Example 5A material (0.65 g) was slurried with an aqueous solution of
- Example 6B material (0.9 g) was slurried with an aqueous solution of Co(N ⁇ 3)2'6H2 ⁇ (0.635 g) and RUCI3 (2 mg) in a rotary evaporator. The water was removed under vacuum at 70°C.
- the dried material was calcined at 250°C under 1500 cc/minute of air.
- the catalyst had a nominal composition of 25 wt. % Co/0.1 wt. % Ru/Si-MCM-41.
- Si-MCM)-41 was dried at 200°C for 30 minutes under flowing N2. It was then mixed thoroughly with C ⁇ 2(CO) (0.2 g) in a glove box. This mixture of solids was placed into a tube furnace boat in a sealed tube and removed from the glove box. It was then heated in a flow of He at 100°C for 15 minutes, raised to 200°C over 10 minutes, then heated at 200°C in He for 30 minutes. The catalyst had a nominal composition of 16 wt. % Co/Si-MCM-41.
- EXAMPLE 10 The procedure was identical to that of Example 9 except that the support was Al-MCM-41.
- the catalyst had a nominal composition of 16 wt. % Co/Al-MCM-41.
- Fischer-Tropsch Processes and Catalysts Using Fluorided Alumina Supports filed May 19, 1999
- U.S. Patent Application No. 09/314,811 entitled Fischer-Tropsch Processes and Catalysts With Promoters, filed May 19, 1999, are hereby incorporated herein in their entirety.
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Abstract
Applications Claiming Priority (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US376873 | 1989-07-07 | ||
US377007 | 1995-01-23 | ||
US9719398P | 1998-08-20 | 1998-08-20 | |
US9719498P | 1998-08-20 | 1998-08-20 | |
US9719298P | 1998-08-20 | 1998-08-20 | |
US97193P | 1998-08-20 | ||
US97194P | 1998-08-20 | ||
US97192P | 1998-08-20 | ||
US37700799A | 1999-08-18 | 1999-08-18 | |
US377008 | 1999-08-18 | ||
US09/376,873 US6319872B1 (en) | 1998-08-20 | 1999-08-18 | Fischer-Tropsch processes using catalysts on mesoporous supports |
US09/377,008 US6235677B1 (en) | 1998-08-20 | 1999-08-18 | Fischer-Tropsch processes using xerogel and aerogel catalysts by destabilizing aqueous colloids |
PCT/US1999/018994 WO2000010698A2 (fr) | 1998-08-20 | 1999-08-19 | Synthese de fischer-tropsch utilisant des catalyseurs sur des supports mesoporeux |
Publications (2)
Publication Number | Publication Date |
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EP1109622A2 true EP1109622A2 (fr) | 2001-06-27 |
EP1109622A4 EP1109622A4 (fr) | 2002-01-23 |
Family
ID=27557542
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99943789A Withdrawn EP1109622A4 (fr) | 1998-08-20 | 1999-08-19 | Synthese de fischer-tropsch utilisant des catalyseurs sur des supports mesoporeux |
EP99942315A Withdrawn EP1128905A1 (fr) | 1998-08-20 | 1999-08-19 | Procedes fischer-tropsch utilisant des catalyseurs a base de xerogel ou d'aerogel formes par la destabilisation de colloides aqueux |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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EP99942315A Withdrawn EP1128905A1 (fr) | 1998-08-20 | 1999-08-19 | Procedes fischer-tropsch utilisant des catalyseurs a base de xerogel ou d'aerogel formes par la destabilisation de colloides aqueux |
Country Status (4)
Country | Link |
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EP (2) | EP1109622A4 (fr) |
AU (3) | AU757374B2 (fr) |
CA (2) | CA2341175A1 (fr) |
WO (3) | WO2000010704A1 (fr) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6548440B1 (en) | 1999-05-26 | 2003-04-15 | Science & Technology Corporation @ Unm | Synthesis of attrition-resistant heterogeneous catalysts using templated mesoporous silica |
US6730708B2 (en) | 2000-07-03 | 2004-05-04 | Conocophillips Company | Fischer-Tropsch processes and catalysts using aluminum borate supports |
CA2428180A1 (fr) | 2000-11-08 | 2002-05-16 | Idemitsu Kosan Co., Ltd. | Catalyseur de reformage pour hydrocarbures et procede de reformage correspondant |
AU2002245459B2 (en) | 2001-01-12 | 2005-10-13 | Conocophillips Company | Boron promoted catalysts and fischer-tropsch processes |
WO2002078840A1 (fr) * | 2001-03-29 | 2002-10-10 | Idemitsu Kosan Co., Ltd. | Catalyseur de reformage d'hydrocarbures et procede de preparation du catalyseur, et procede de reformage d'hydrocarbures mettant en oeuvre ledit catalyseur |
US7067453B1 (en) | 2001-07-13 | 2006-06-27 | Innovatek, Inc. | Hydrocarbon fuel reforming catalyst and use thereof |
EP2666540A1 (fr) * | 2012-05-22 | 2013-11-27 | Karlsruher Institut für Technologie | Procédé d'hydrodésoxygénation catalytique de dérivés de furane et/ou d'huiles de pyrolyse, le catalyseur correspondant et son procédé de préparation. |
US10875820B2 (en) | 2013-06-20 | 2020-12-29 | Standard Alcohol Company Of America, Inc. | Catalyst for converting syngas to mixed alcohols |
US9290425B2 (en) * | 2013-06-20 | 2016-03-22 | Standard Alcohol Company Of America, Inc. | Production of mixed alcohols from synthesis gas |
FR3018810B1 (fr) | 2014-03-20 | 2017-06-09 | Ifp Energies Now | Procede fischer-tropsch utilisant un catalyseur a base d'un metal du groupe viiib et d'un support d'oxydes comprenant de l'alumine, de la silice et du phosphore |
CN111375439B (zh) * | 2020-04-22 | 2022-09-20 | 陕西延长石油(集团)有限责任公司 | 一种液相丙烯一步制备环氧丙烷的方法及催化剂 |
CN112517019A (zh) * | 2020-12-17 | 2021-03-19 | 大唐国际化工技术研究院有限公司 | 一种以TiO2气凝胶为载体的甲烷化催化剂及其制备方法和应用 |
CN112588292A (zh) * | 2020-12-17 | 2021-04-02 | 大唐国际化工技术研究院有限公司 | 一种以TiO2气凝胶为载体的甲烷化催化剂及其制备方法和应用 |
CN114671452B (zh) * | 2022-03-03 | 2023-09-01 | 滁州学院 | 一种以环氧化合物为凝胶促进剂制备块状氧化铈气凝胶的方法 |
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WO2000073205A1 (fr) * | 1999-06-02 | 2000-12-07 | The Board Of Regents Of The University Of Oklahoma | Procede de production de nanotubes en carbone et catalyseurs appropries |
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US4469814A (en) * | 1982-12-10 | 1984-09-04 | Coal Industry (Patents) Limited | Catalysts |
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US5395805A (en) * | 1993-03-25 | 1995-03-07 | Regents Of The University Of California | Method for making monolithic metal oxide aerogels |
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1999
- 1999-08-19 EP EP99943789A patent/EP1109622A4/fr not_active Withdrawn
- 1999-08-19 WO PCT/US1999/018895 patent/WO2000010704A1/fr not_active Application Discontinuation
- 1999-08-19 AU AU56818/99A patent/AU757374B2/en not_active Ceased
- 1999-08-19 CA CA002341175A patent/CA2341175A1/fr not_active Abandoned
- 1999-08-19 EP EP99942315A patent/EP1128905A1/fr not_active Withdrawn
- 1999-08-19 AU AU55721/99A patent/AU746882B2/en not_active Ceased
- 1999-08-19 CA CA002341174A patent/CA2341174A1/fr not_active Abandoned
- 1999-08-19 AU AU55751/99A patent/AU5575199A/en not_active Abandoned
- 1999-08-19 WO PCT/US1999/018994 patent/WO2000010698A2/fr active IP Right Grant
- 1999-08-19 WO PCT/US1999/018962 patent/WO2000010705A1/fr active Application Filing
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US5028634A (en) * | 1989-08-23 | 1991-07-02 | Exxon Research & Engineering Company | Two stage process for hydrocarbon synthesis |
WO1993001884A1 (fr) * | 1991-07-24 | 1993-02-04 | Mobil Oil Corporation | Catalyseur d'hydrotraitement |
US5302622A (en) * | 1992-07-27 | 1994-04-12 | Institut Francais Du Petrole | Cobalt-based catalyst and process for converting synthesis gas into hydrocarbons |
EP0911079A2 (fr) * | 1997-10-17 | 1999-04-28 | Hoechst Research & Technology Deutschland GmbH & Co. KG | Catalyseurs supportés présentant une résistance améliorée au frittage et leur méthode de préparation |
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Also Published As
Publication number | Publication date |
---|---|
AU5575199A (en) | 2000-03-14 |
WO2000010698A2 (fr) | 2000-03-02 |
AU746882B2 (en) | 2002-05-02 |
WO2000010705A1 (fr) | 2000-03-02 |
CA2341174A1 (fr) | 2000-03-02 |
EP1109622A4 (fr) | 2002-01-23 |
AU5681899A (en) | 2000-03-14 |
EP1128905A1 (fr) | 2001-09-05 |
CA2341175A1 (fr) | 2000-03-02 |
AU5572199A (en) | 2000-03-14 |
WO2000010704A1 (fr) | 2000-03-02 |
WO2000010698A3 (fr) | 2000-10-26 |
AU757374B2 (en) | 2003-02-20 |
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