NO317854B1 - Katalysator, fremgangsmate for fremstilling derav, anvendelse derav og fremgangsmate for fremstilling av hydrokarboner. - Google Patents
Katalysator, fremgangsmate for fremstilling derav, anvendelse derav og fremgangsmate for fremstilling av hydrokarboner. Download PDFInfo
- Publication number
- NO317854B1 NO317854B1 NO19975881A NO975881A NO317854B1 NO 317854 B1 NO317854 B1 NO 317854B1 NO 19975881 A NO19975881 A NO 19975881A NO 975881 A NO975881 A NO 975881A NO 317854 B1 NO317854 B1 NO 317854B1
- Authority
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- Norway
- Prior art keywords
- cobalt
- catalyst
- manganese
- molar ratio
- hydrocarbons
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 31
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 24
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000010941 cobalt Substances 0.000 claims abstract description 55
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 53
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 30
- 239000011572 manganese Substances 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 5
- 239000007789 gas Substances 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 5
- 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 5
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000012190 activator Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical class [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910052702 rhenium Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- XEUFSQHGFWJHAP-UHFFFAOYSA-N cobalt(2+) manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Co++] XEUFSQHGFWJHAP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 2
- 229910003452 thorium oxide Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- AMUZOYIZFAFTKF-UHFFFAOYSA-N [O-2].[V+5].[Co+2] Chemical compound [O-2].[V+5].[Co+2] AMUZOYIZFAFTKF-UHFFFAOYSA-N 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- -1 copper-activated cobalt manganese Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor 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
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
-
- 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
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C2521/08—Silica
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/20—Vanadium, niobium or tantalum
- C07C2523/22—Vanadium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/32—Manganese, technetium or rhenium
- C07C2523/34—Manganese
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tatalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/656—Manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/75—Cobalt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/847—Vanadium, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/889—Manganese, technetium or rhenium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95201644 | 1995-06-16 | ||
| PCT/EP1996/002577 WO1997000231A1 (en) | 1995-06-16 | 1996-06-12 | Catalyst and process for the preparation of hydrocarbons |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO975881D0 NO975881D0 (no) | 1997-12-15 |
| NO975881L NO975881L (no) | 1997-12-15 |
| NO317854B1 true NO317854B1 (no) | 2004-12-20 |
Family
ID=8220390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO19975881A NO317854B1 (no) | 1995-06-16 | 1997-12-15 | Katalysator, fremgangsmate for fremstilling derav, anvendelse derav og fremgangsmate for fremstilling av hydrokarboner. |
Country Status (20)
| Country | Link |
|---|---|
| US (1) | US5981608A (zh) |
| EP (1) | EP0833807B1 (zh) |
| JP (1) | JP4319701B2 (zh) |
| KR (1) | KR100447463B1 (zh) |
| CN (1) | CN1087193C (zh) |
| AU (1) | AU698391B2 (zh) |
| BR (1) | BR9608451A (zh) |
| CA (1) | CA2224690C (zh) |
| DE (1) | DE69632189T2 (zh) |
| DK (1) | DK0833807T3 (zh) |
| DZ (1) | DZ2051A1 (zh) |
| EA (1) | EA000319B1 (zh) |
| ES (1) | ES2215194T3 (zh) |
| MY (1) | MY117350A (zh) |
| NO (1) | NO317854B1 (zh) |
| NZ (1) | NZ311669A (zh) |
| PE (1) | PE12497A1 (zh) |
| TW (1) | TW349882B (zh) |
| WO (1) | WO1997000231A1 (zh) |
| ZA (1) | ZA965078B (zh) |
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| US6475943B1 (en) * | 1995-11-08 | 2002-11-05 | Shell Oil Company | Catalyst activation process |
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| ES2221235T3 (es) * | 1997-12-30 | 2004-12-16 | Shell Internationale Research Maatschappij B.V. | Catalizador de fischer-trosch a base de cobalto. |
| US6368997B2 (en) * | 1998-05-22 | 2002-04-09 | Conoco Inc. | Fischer-Tropsch processes and catalysts using fluorided supports |
| US6365544B2 (en) * | 1998-05-22 | 2002-04-02 | Conoco Inc. | Fischer-Tropsch processes and catalysts using fluorided alumina supports |
| US6596915B1 (en) * | 1999-09-22 | 2003-07-22 | Carrier Corporation | Catalysts for destruction of organophosphonate compounds |
| US6313062B1 (en) * | 1999-10-29 | 2001-11-06 | Exxon Reserach And Engineering Company | Process for the preparation of high activity carbon monoxide hydrogenation catalysts; the catalyst composition, use of the catalysts for conducting such reactions, and the products of such reactions |
| AU2000246479A1 (en) * | 2000-04-07 | 2001-10-23 | Phillips Petroleum Company | Process for preparing fischer-tropsch catalyst |
| MXPA02012731A (es) | 2000-07-03 | 2003-05-14 | Shell Int Research | Catalizador y proceso para la preparacion de hidrocarburos. |
| US6521565B1 (en) * | 2000-08-01 | 2003-02-18 | Exxonmobil Research And Engineering Company | Cobalt catalyst compositions useful for conducting carbon monoxide hydrogenation reactions |
| US20030105170A1 (en) * | 2001-09-21 | 2003-06-05 | Conoco Inc. | Surface area of cobalt catalyst supported by silica carrier material |
| US7001927B2 (en) * | 2001-12-28 | 2006-02-21 | Conocophillips Company | Water removal in Fischer-Tropsch processes |
| US6956063B2 (en) * | 2001-12-28 | 2005-10-18 | Conocophillips Company | Method for reducing water concentration in a multi-phase column reactor |
| US6809122B2 (en) * | 2001-12-28 | 2004-10-26 | Conocophillips Company | Method for reducing the maximum water concentration in a multi-phase column reactor |
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| US20050119119A1 (en) * | 2003-12-02 | 2005-06-02 | Rogers David B. | Water gas shift catalyst on a lanthanum-doped anatase titanium dioxide support for fuel cells application |
| US20050119118A1 (en) * | 2003-12-02 | 2005-06-02 | Walsh Troy L. | Water gas shift catalyst for fuel cells application |
| EP1807198B1 (en) | 2004-11-03 | 2011-02-16 | Shell Internationale Research Maatschappij B.V. | Synthesis of hydrocarbons using titania catalysts |
| DE102004054959A1 (de) * | 2004-11-13 | 2006-05-18 | Bayer Technology Services Gmbh | Katalysator zur Herstellung von Kohlenstoffnanoröhrchen durch Zersetzung von gas-förmigen Kohlenverbindungen an einem heterogenen Katalysator |
| DE102004058780A1 (de) * | 2004-12-07 | 2006-06-08 | Robert Bosch Gmbh | Katalysator zur Oxidation kohlenstoffhaltiger Partikel und Vorrichtung zur Reinigung von Gasgemischen diesen enthaltend |
| AU2005318138B2 (en) | 2004-12-23 | 2009-08-06 | Shell Internationale Research Maatschappij B.V. | Process for preparing a catalyst |
| AU2006325209B2 (en) | 2005-12-16 | 2010-11-04 | Shell Internationale Research Maatschappij B.V. | Process for preparing a hydrocarbon synthesis catalyst |
| AR061824A1 (es) * | 2006-07-10 | 2008-09-24 | Shell Int Research | Metodo para soportar un material catalizador de sintesis de hidrocarburos |
| WO2008061970A2 (en) | 2006-11-22 | 2008-05-29 | Shell Internationale Research Maatschappij B.V. | Process for hydrocarbon synthesis |
| EP2097167A2 (en) * | 2006-12-12 | 2009-09-09 | Shell Internationale Research Maatschappij B.V. | Process for preparing a catalyst |
| WO2008090105A2 (en) * | 2007-01-23 | 2008-07-31 | Shell Internationale Research Maatschappij B.V. | Process for preparing a catalyst |
| US20080260631A1 (en) | 2007-04-18 | 2008-10-23 | H2Gen Innovations, Inc. | Hydrogen production process |
| EP2075314A1 (en) | 2007-12-11 | 2009-07-01 | Shell Internationale Research Maatschappij B.V. | Grease formulations |
| EP2078743A1 (en) | 2008-01-10 | 2009-07-15 | Shell Internationale Researchmaatschappij B.V. | Fuel composition |
| AU2009228933B2 (en) | 2008-03-28 | 2012-05-31 | Shell Internationale Research Maatschappij B.V. | Process for regenerating a catalyst |
| CN101590411B (zh) * | 2008-05-28 | 2012-11-07 | 北京三聚环保新材料股份有限公司 | 一种非贵金属加氢催化剂及其制备方法 |
| AU2010338450B2 (en) | 2009-12-16 | 2013-06-27 | Shell Internationale Research Maatschappij B.V. | Process for regenerating a catalyst |
| US8980194B2 (en) | 2009-12-28 | 2015-03-17 | Shell Oil Company | Stacked catalyst bed for Fischer-Tropsch |
| EP2186783A3 (en) | 2010-01-27 | 2010-09-01 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of olefins |
| EP2186784A3 (en) | 2010-01-27 | 2010-09-01 | Shell Internationale Research Maatschappij B.V. | Process for the preparation and recovery of olefins |
| EP2186785A3 (en) | 2010-01-27 | 2010-09-01 | Shell Internationale Research Maatschappij B.V. | Process for the separation of olefins from paraffins |
| JP5730495B2 (ja) * | 2010-03-30 | 2015-06-10 | 独立行政法人石油天然ガス・金属鉱物資源機構 | フィッシャー・トロプシュ合成反応用活性化触媒の製造方法、触媒スラリーの製造方法、並びに触媒スラリーのフィッシャー・トロプッシュ合成反応器への供給方法 |
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| EP2655553A1 (en) | 2010-12-22 | 2013-10-30 | Saudi Basic Industries Corporation | Catalyst useful in fisher-tropsch synthesis |
| EP2468394A1 (en) | 2010-12-23 | 2012-06-27 | Shell Internationale Research Maatschappij B.V. | Multi-tubular fixed bed reactor and its use |
| US8729140B2 (en) | 2010-12-23 | 2014-05-20 | Shell Oil Company | Process for regenerating a catalyst |
| WO2013000962A1 (en) | 2011-06-28 | 2013-01-03 | Shell Internationale Research Maatschappij B.V. | Stacked catalyst bed for fischer-tropsch |
| BR112013033778A2 (pt) | 2011-06-28 | 2017-02-07 | Shell Int Research | tubo reator, reação de fischer tropsch, e, processo para realizar uma parada de alta velocidade em um processo de fischer-tropsch |
| US9234139B2 (en) | 2011-11-01 | 2016-01-12 | Accelergy Corporation | Diesel fuel production process employing direct and indirect coal liquefaction |
| EP2864456B1 (en) | 2012-06-21 | 2018-10-31 | Shell International Research Maatschappij B.V. | Lubricating oil compositions comprising heavy fischer-tropsch derived base oils and alkylated aromatic base oil |
| EP2679568A1 (en) | 2012-06-25 | 2014-01-01 | Saudi Basic Industries Corporation | Process for production ethylene and propylene from syngas |
| EA029026B1 (ru) * | 2012-06-27 | 2018-01-31 | Сауди Бейсик Индастриз Корпорейшн | Катализатор и способ селективного получения низших углеводородов с1-с5 из синтез-газа с низким выходом метана и co |
| KR101405518B1 (ko) | 2013-05-22 | 2014-06-11 | 한국과학기술연구원 | 피셔-트롭시 합성반응용 코발트계 촉매의 제조방법 |
| WO2015010941A1 (en) | 2013-07-24 | 2015-01-29 | Shell Internationale Research Maatschappij B.V. | Process for preparing a chlorine comprising catalyst, the prepared catalyst, and its use |
| US20160160128A1 (en) | 2013-07-24 | 2016-06-09 | Shell Oil Company | Method for starting up a fischer tropsch process |
| EP3024577A1 (en) | 2013-07-24 | 2016-06-01 | Shell Internationale Research Maatschappij B.V. | Process for preparing a chlorine comprising catalyst, the prepared catalyst, and its use |
| WO2015015316A2 (en) | 2013-07-31 | 2015-02-05 | Saudi Basic Industies Corporation | Catalyst for conversion of synthesis gas |
| AP2016009185A0 (en) | 2013-11-08 | 2016-04-30 | Shell Int Research | Process for catalyst unloading facilitation |
| JP6007167B2 (ja) * | 2013-11-18 | 2016-10-12 | Ｊｘエネルギー株式会社 | フィッシャー・トロプシュ合成用触媒の製造方法及び炭化水素の製造方法 |
| AP2016009375A0 (en) | 2014-03-17 | 2016-08-31 | Shell Int Research | A method for start-up and operation of a fischer-tropsch reactor |
| EP2921546A1 (en) | 2014-03-17 | 2015-09-23 | Shell International Research Maatschappij B.V. | A method for start-up of a Fischer-Tropsch reactor |
| CN106103657B (zh) | 2014-03-17 | 2018-10-23 | 国际壳牌研究有限公司 | 费-托反应器的开车和操作方法 |
| EP2940102A1 (en) | 2014-05-01 | 2015-11-04 | Shell International Research Maatschappij B.V. | A method for start-up and operation of a Fischer-Tropsch reactor |
| AU2015359691B2 (en) * | 2014-12-12 | 2020-11-19 | Bp P.L.C. | Fischer-Tropsch process using reductively-activated cobalt catalyst |
| JP6824168B2 (ja) | 2014-12-19 | 2021-02-03 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイＳｈｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌｅ Ｒｅｓｅａｒｃｈ Ｍａａｔｓｃｈａｐｐｉｊ Ｂｅｓｌｏｔｅｎ Ｖｅｎｎｏｏｔｓｈａｐ | 触媒の調製方法 |
| MY194211A (en) | 2015-09-04 | 2022-11-21 | Shell Int Research | Method of manufacturing hydrocarbons |
| EP3344729B1 (en) | 2015-09-04 | 2019-12-11 | Shell International Research Maatschappij B.V. | Process to prepare paraffins and waxes |
| AU2016376824B2 (en) | 2015-12-21 | 2020-04-30 | Shell Internationale Research Maatschappij B.V. | Hydrogenation catalyst and method for preparing the same |
| MY197616A (en) | 2016-11-07 | 2023-06-28 | Shell Int Research | Method of producing hydrocarbons |
| AU2019219056B2 (en) | 2018-02-09 | 2024-04-18 | Bp P.L.C. | Fischer-Tropsch process, supported Fischer-Tropsch synthesis catalyst and uses thereof |
| EP3628400A1 (en) | 2018-09-26 | 2020-04-01 | Bp P.L.C. | Fischer-tropsch process, supported fischer-tropsch synthesis catalyst and uses thereof |
| CN111867725A (zh) | 2018-03-20 | 2020-10-30 | 国际壳牌研究有限公司 | 含钴催化剂的制备 |
| US12043591B2 (en) | 2018-09-28 | 2024-07-23 | Bp P.L.C. | Fischer-tropsch process |
| GB201903502D0 (en) | 2019-03-14 | 2019-05-01 | Johnson Matthey Plc | Cobalt catalysts and precursors therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2026657A1 (en) * | 1970-06-01 | 1972-01-27 | Heinrich Koppers Gmbh, 4300 Essen | Catalytic combustion of ammonia - to nitrogen and water , using excess oxygen over cobalt/copper oxide |
| US3912763A (en) * | 1973-07-19 | 1975-10-14 | Phillips Petroleum Co | Oxidative dehydrogenation of alkenes or alkadienes to furan compounds |
| US4588708A (en) * | 1985-04-15 | 1986-05-13 | Kansas State University Research Foundation | Bimetallic solvated metal atom dispersed catalysts |
| CA1340441C (en) * | 1988-04-25 | 1999-03-16 | Chang Jung Kim | Water addition for increased co/h2 hydrocarbon synthesis activity over catalysts comprising rhenium promoted cobalt on titania |
| GB2256375B (en) * | 1991-05-31 | 1995-06-07 | Riken Kk | Exhaust gas cleaner and method of cleaning exhaust gas |
| US5162284A (en) * | 1991-08-05 | 1992-11-10 | Exxon Research And Engineering Co. | Copper promoted cobalt-manganese spinel catalyst and method for making the catalyst for Fischer-Tropsch synthesis |
| WO1993005000A1 (en) * | 1991-08-28 | 1993-03-18 | The Broken Hill Proprietary Company Limited | Fischer tropsch catalyst comprising cobalt and scandium |
| DE4325847A1 (de) * | 1993-07-31 | 1995-02-02 | Basf Ag | Kobaltkatalysatoren |
-
1996
- 1996-06-12 EP EP96921991A patent/EP0833807B1/en not_active Expired - Lifetime
- 1996-06-12 CN CN96194640A patent/CN1087193C/zh not_active Expired - Fee Related
- 1996-06-12 DK DK96921991T patent/DK0833807T3/da active
- 1996-06-12 WO PCT/EP1996/002577 patent/WO1997000231A1/en active IP Right Grant
- 1996-06-12 DZ DZ960095A patent/DZ2051A1/fr active
- 1996-06-12 DE DE69632189T patent/DE69632189T2/de not_active Expired - Lifetime
- 1996-06-12 CA CA002224690A patent/CA2224690C/en not_active Expired - Fee Related
- 1996-06-12 JP JP50264797A patent/JP4319701B2/ja not_active Expired - Fee Related
- 1996-06-12 KR KR1019970709450A patent/KR100447463B1/ko not_active IP Right Cessation
- 1996-06-12 NZ NZ311669A patent/NZ311669A/xx unknown
- 1996-06-12 ES ES96921991T patent/ES2215194T3/es not_active Expired - Lifetime
- 1996-06-12 AU AU63033/96A patent/AU698391B2/en not_active Ceased
- 1996-06-12 BR BR9608451A patent/BR9608451A/pt not_active Application Discontinuation
- 1996-06-12 EA EA199800068A patent/EA000319B1/ru not_active IP Right Cessation
- 1996-06-14 MY MYPI96002412A patent/MY117350A/en unknown
- 1996-06-14 ZA ZA965078A patent/ZA965078B/xx unknown
- 1996-06-17 PE PE1996000466A patent/PE12497A1/es not_active Application Discontinuation
- 1996-07-17 TW TW085108681A patent/TW349882B/zh active
-
1997
- 1997-12-15 NO NO19975881A patent/NO317854B1/no not_active IP Right Cessation
-
1998
- 1998-07-28 US US09/123,711 patent/US5981608A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CA2224690A1 (en) | 1997-01-03 |
| EP0833807A1 (en) | 1998-04-08 |
| NO975881D0 (no) | 1997-12-15 |
| DE69632189D1 (de) | 2004-05-19 |
| EA199800068A1 (ru) | 1998-08-27 |
| ES2215194T3 (es) | 2004-10-01 |
| CA2224690C (en) | 2007-06-05 |
| CN1087193C (zh) | 2002-07-10 |
| AU6303396A (en) | 1997-01-15 |
| KR100447463B1 (ko) | 2004-10-14 |
| US5981608A (en) | 1999-11-09 |
| AU698391B2 (en) | 1998-10-29 |
| TW349882B (en) | 1999-01-11 |
| NO975881L (no) | 1997-12-15 |
| EA000319B1 (ru) | 1999-04-29 |
| NZ311669A (en) | 1998-12-23 |
| DE69632189T2 (de) | 2005-04-21 |
| ZA965078B (en) | 1997-01-23 |
| JP4319701B2 (ja) | 2009-08-26 |
| DZ2051A1 (fr) | 2002-10-23 |
| BR9608451A (pt) | 1999-01-05 |
| EP0833807B1 (en) | 2004-04-14 |
| MX9710023A (es) | 1998-07-31 |
| MY117350A (en) | 2004-06-30 |
| WO1997000231A1 (en) | 1997-01-03 |
| CN1187180A (zh) | 1998-07-08 |
| KR19990022980A (ko) | 1999-03-25 |
| PE12497A1 (es) | 1997-05-09 |
| DK0833807T3 (da) | 2004-05-17 |
| JPH11507866A (ja) | 1999-07-13 |
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