WO2005085390A1 - Cobalt catalyst for the synthesis of fischer-tropsch, catalyst support, processes for the preparation of support and catalyst and the use of the catalyst - Google Patents
Cobalt catalyst for the synthesis of fischer-tropsch, catalyst support, processes for the preparation of support and catalyst and the use of the catalyst Download PDFInfo
- Publication number
- WO2005085390A1 WO2005085390A1 PCT/BR2005/000028 BR2005000028W WO2005085390A1 WO 2005085390 A1 WO2005085390 A1 WO 2005085390A1 BR 2005000028 W BR2005000028 W BR 2005000028W WO 2005085390 A1 WO2005085390 A1 WO 2005085390A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- cobalt
- range
- support
- niobium
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 59
- 239000010941 cobalt Substances 0.000 title claims abstract description 59
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 24
- 230000008569 process Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 56
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 28
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000010955 niobium Substances 0.000 claims abstract description 12
- 150000001336 alkenes Chemical class 0.000 claims abstract description 11
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 11
- 239000002283 diesel fuel Substances 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 34
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 33
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 230000009467 reduction Effects 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 19
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229910000335 cobalt(II) sulfate Inorganic materials 0.000 claims description 3
- PKSIZOUDEUREFF-UHFFFAOYSA-N cobalt;dihydrate Chemical compound O.O.[Co] PKSIZOUDEUREFF-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims description 2
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 claims description 2
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 2
- 229960005235 piperonyl butoxide Drugs 0.000 claims description 2
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims description 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000003049 inorganic solvent Substances 0.000 claims 1
- -1 niobium alkoxides Chemical class 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims 1
- 239000000243 solution Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 238000001994 activation Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000004913 activation Effects 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 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
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- OHZZTXYKLXZFSZ-UHFFFAOYSA-I manganese(3+) 5,10,15-tris(1-methylpyridin-1-ium-4-yl)-20-(1-methylpyridin-4-ylidene)porphyrin-22-ide pentachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mn+3].C1=CN(C)C=CC1=C1C(C=C2)=NC2=C(C=2C=C[N+](C)=CC=2)C([N-]2)=CC=C2C(C=2C=C[N+](C)=CC=2)=C(C=C2)N=C2C(C=2C=C[N+](C)=CC=2)=C2N=C1C=C2 OHZZTXYKLXZFSZ-UHFFFAOYSA-I 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
-
- 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
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8474—Niobium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—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
- C10G2/332—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 iron-group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/613—
-
- B01J35/615—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
- C01P2006/13—Surface area thermal stability thereof at high temperatures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
Definitions
- the invention relates to a cobalt catalyst supported on a high- surface area niobium pentoxide, the processes for making the support and the catalyst itself, the use of the support for making the catalyst and the use of the catalyst for the Fischer-Tropsch synthesis (FTS).
- FTS Fischer-Tropsch synthesis
- the Fischer-Tropsch synthesis consists of the chemical conversion of synthesis gas (CO and H 2 ) in a mixture of hydrocarbons, which composition depends upon the type of catalyst used and the reaction conditions. Typically, light hydrocarbons (Ci to C 4 ), linear or branched paraffin in the range of gasoline and diesel fuels (C 5 -C1 9 ), alpha-olefins, heavy waxes (C ⁇ 9 + ) and oxygenated compounds can be obtained.
- the most employed catalysts comprise, as active metal, iron (Fe), cobalt (Co), ruthenium (Ru) and mixtures thereof, supported or not in metal oxides.
- cobalt catalysts present the best performance in terms of productivity and selectivity to hydrocarbons of C5 composition. Liquid fuels, gasoline and diesel, are found in this fraction.
- the preparation method the nature of cobalt precursor salts, the support, the cobalt content, the presence of promoters and pretreatment conditions for calcination, reduction and activation are important parameters to guarantee the performance of the catalytic material.
- the most common supports for cobalt catalysts are silica (Si0 2 ) and alumina (A1 0 3 ).
- Alternative supports such as titania (Ti0 2 ) are also used due to their capacity of forming intermetallic compounds with Lewis acid-base properties.
- SMSI strong metal-support interaction
- U.S. Samuel J. Tauster
- Patent 4,149,998 who observed the suppression of chemisorption capacity of hydrogen (H 2 ) and carbon monoxide (CO) by Group VIIIB elements when supported in Ti0 2 , V 2 0 5 , Ce0 2 , Nb 2 0 5 , among others. As a result, the activity and selectivity of reactions that involve the adsorption-desorption of H 2 and CO were significantly altered.
- the present invention takes advantage of SMSI properties of Nb 2 0 5 -supported cobalt catalyst by "using a high-surface area niobium pentoxide support to promote its activity ⁇ , selectivity and stability towards a higher fraction of hydrocarbons of C 5 + composition, very selective to diesel fuel fraction, with negligible formation of branched, unsaturated and oxygenated compounds.
- the present invention describes the prep aration of a catalyst and its use in the Fischer-Tropsch synthesis.
- the catalyst comprises cobalt supported on a high-surface area niobium pentoxide (Nb 2 0 5 ) in powdery form with a well- defined particle size distribution, pellets or extrudates. It is highly selective to C 5 + hydrocarbons, which composition is very rich in diesel (C 12 -C 19 ). In addition, the catalyst does not produce a significant amount of olefins and oxygenated compounds.
- the catalyst in its oxide form is activated, prior to the utilization on FTS, through reduction of cobalt oxide to metal cobalt by exposing it to a reducing atmosphere comprising either hydrogen (H 2 ) or carbon monoxide (CO) at a suitable temperature that guarantees thorough cobalt oxide reduction.
- the reduced catalyst may be or not passivated to further u_se on FTS without the need of another reduction.
- the SMSI state is formed, indicated by the presence of non-stoichiorne ⁇ tric niobium oxides (NbO x ) in the interface Co-Nb 2 0 5 .
- the extent of reduction of the niobium pentoxide is a function of the temperature.
- the activated catalyst is then submitted to reaction conditions by introducing synthesis gas (CO and H 2 mixture) at a suitable time, temperature and pressure to higher activity and selectivity to Cs + hydrocarbons, specially in diesel fuel fraction, with minimal production of olefin and oxygenated compounds.
- synthesis gas CO and H 2 mixture
- One goal of the present invention is a cobalt catalyst for Fischer- Tropsch synthesis supported on a high-surface area niobium pentoxide with a content of metal cobalt in the final composition of the catalyst supported on niobium pentoxide in the range of 3 to 40 wt.%, preferentially in the range of 4 to 25 wt.% and more preferentially in the range of 5 to 15 wt.%.
- the catalyst for FTS might be exposed to the action of a reducing gas comprising either hydrogen (H 2 ), carbon monoxide (CO) or mixtures thereof, the hydrogen being the preferential reducing gas, at a reduction temperature between 300 to 600°C, preferentially between 350 to 550°C and more preferentially between 400 to 500°C.
- the reduction time is no less than 6 hours, preferentially between 10 to 24 hrs and more preferentially between 14 and 20 hrs.
- the cobalt catalyst in accordance with the invention is obtained from soluble precursors such as cobalt (II) nitrate [Co(N0 3 ) 2 .6H 2 0], cobalt (II) chloride (CoCl 2 .6H 2 0), cobalt (II) sulfate (CoS0 4 .xH 2 0), cobalt (II) hydroxide [Co(OH) 2 ] and cobalt (II) acetate [(CH 3 C0 2 ) 2 Co], the cobalt nitrate and chloride, and more preferred the cobalt nitrate, being preferred as soluble precursors.
- cobalt (II) nitrate Co(N0 3 ) 2 .6H 2 0
- cobalt (II) chloride CoCl 2 .6H 2 0
- cobalt (II) sulfate CoS0 4 .xH 2 0
- Another goal of the invention is the support for the catalyst for FTS, which consists of a high-surface area niobim pentoxide (Nb 2 0 5 ) with BET surface area in the range of 30 to 160 m 2 .g _1 , preferentially between 60 to 150 m 2 .g _1 and more preferentially between 80 to 100 m 2 .g _1 , and presenting as crystal structure the pseudo-hexagonal phase.
- Nb 2 0 5 niobim pentoxide
- a further goal of the invention is the process of preparation of the high-surface area niobium pentoxide as a catalyst support that involves the calcination of hydrated niobium oxide at temperatures between 200 to 800°C for a period of 2 to 4 hours. Preferentially the calcination is carried out between 300 to 700°C and more preferentially between 400 to 600°C.
- Another process of preparation of the catalyst support of niobium pentoxide consists of the synthesis of niobium pentoxide from precipitation or sol-gel of either organic or inorganic niobium precursors such as niobium oxalate, pentachloride and alkoxides (methoxide, isopropoxide and butoxide).
- the solvents employed in the preparation of the cobalt precursor solution are water, methanol, ethanol, propanol, isopropanol and acetone, preferentially water, methanol, ethanol and isopropanol and more preferentially water and ethanol.
- the step of support impregnation can be done or selected among several techniques such as incipient wetness impregnation, wet impregnation and deposition-precipitation.
- Another goal of this invention is the use of Nb 2 0 5 -supported cobalt catalyst for the Fischer-Tropsch synthesis to obtain hydrocarbons with carbon atoms equal or higher than 5 (five), the so-called C 5 + fraction, containing preferentially linear parafins in the fraction of diesel oil, with minimal formation of light hydrocarbons, olefins, aromatics and oxygenated compounds.
- the selectivity to C 5 + hydrocarbons is superior to 70 wt.%, and the fraction in the diesel oil range (C ⁇ 2 -C ⁇ 8 ) is higher than 80 wt.%, the formation of light hydrocarbons (C0 2 , CH , C 2 -C 4 ), olefins, aromatics and oxygenated compounds are less than 10 wt.%.
- the catalyst is active and selective to produce hydrocarbons through the reaction of a mixture of carbon monoxide (CO) and hydrogen (H 2 ) with a pre-defined H 2 /CO ratio, temperature, pressure and space velocity suitable to a more selective production of hydrocarbons with carbon atoms equal or higher than 5 (Cs + ).
- the H 2 /CO volumetric ratio of the reaction is preferentially in the range of 1 to 3, more preferentially in the range of 1.5 to 2.5, and even more preferentially in the range of 1.8 to 2.2.
- the reaction temperature varies from 200 to 300°C, preferentially from 200 to 250°C, and more preferentially from 210 to 240°C.
- the reaction pressure varies from 405 to 5,000 kPa, preferentially from 1,500 to 4,000 kPa and more preferentially from 1,800 to 2,200 kPa.
- the space velocity of the reaction is in the range of 100 to 6,000 h "1 , preferentially from 300 to 2,000 h "1 and more preferentially from 400 to 1,000 h "1 .
- FIG. 1 X-ray diffraction of niobium pentoxide: as-prepared Nb 2 0 5 and calcined Nb 2 0 5 at 500°C.
- FIG. 2 BET surface area of niobium pentoxide as function of calcination temperature.
- FIG. 3 TPR profile of catalysts showing the formation of SMSI effect between particles of Co and support of Nb 2 0 5 .
- FIG. 4 Distillation of Fischer-Tropsch hydrocarbon liquid fraction obtained according to one of the prepared catalysts.
- the high-surface area support of niobium pentoxide can be obtained by the calcination of a hydrated niobium oxide (Nb 2 0 5 .nH 2 0), for instance, the commercial HY® niobia from CBMM (Companhia Brasileira de Metalurgia e Mineracao) with a water content in the range of 15 to 25 wt.%.
- the support of niobium pentoxide can also be obtained by synthesis techniques such as precipitation and sol-gel from the use of either organic or inorganic niobium precursors.
- the hydrated niobium oxide is an amorphous material as shown its X-ray diffraction pattern ( Figure 1) with a BET surface area around 160 m .gX
- the thermal treatment of this material causes the loss of surface area as a function of calcination temperature as indicated in Figure 2. Above 500°C, the loss of surface area is significant, reaching values lower than 30 m 2 .g _1 .
- the loss of surface area is attributed to water removal and the crystallization process of the amorphous material.
- X-ray diffraction pattern of ttie calcined material at 500°C reveals a material with a low degree of crystalliza,tion, pseudo-hexagonal structure and lamellar morphology.
- the surface area of Nb 2 0 5 which is a function of calcination temperature, is in the range of 30 to 1 1 9 1 160 m .g " , preferentially between 60 and 150 m .g " , and more preferentially around 80 to lOO rr ⁇ g "1 ,
- the niobium pentoxide prepared by the calcination of a hydrated niobium oxide is impregnated by a solution of cobalt precursors.
- the cobalt precursors used are cobalt (II) nitrate [Co(N0 3 ) 2 .6H 2 0], cobalt (II) chloride (CoCl 2 .6H 2 0), cobalt (II) sulfate (CoS0 4 .xH 2 0), cobalt (II) hydroxide [Co(OH) 2 ] and cobalt (II) acetate [(CH 3 C0 2 ) 2 Co], preferentially cobalt nitrate and cobalt chloride, and more preferentially cobalt nitrate.
- the solvents employed in the preparation of the impregnating solution are water (H 2 0), methanol (CH 3 OH), ethanol (CH 3 CH 2 OH), propanol (CH 3 CH 2 CH 2 OH), isopropanol (CH 3 CHOHCH 3 ) and acetone (CH 3 COCH 3 ).
- the preferred solvents are water, methanol, ethanol and isopropanol, and the more preferred solvents are water and ethanol.
- the amount of cobalt precursor added to the impregnating solution is a function of the desirable final content of metal cobalt in the composition of the catalyst.
- the metal cobalt content varies from 3 to 40 wt.%, preferentially between 4 and 25 wt.%, and more preferentially between 5 and 15 wt.%.
- the catalyst preparation techniques employed are selected among many known in the art such as wet impregnation, incipient wetness impregnation and deposition-precipitation, preferentially wet impregnation and incipient wetness impregnation, and more preferentially the incipient wetness impregnation.
- the volume of the impregnating solution must have the same pore volume of niobium pentoxide.
- Nb 2 ⁇ 5 pore volume is done by water titration, in which a known amount of the support, for instance, 100 g, suffers gradual dropping up to a point the powdery support becomes a mud-like cake. The amount of water added before reaching the mud-like cake point is the solution volume corresponding to the pore volume of the support. This volume is the impregnating volume used to prepare the cobalt (II) nitrate solution. The addition of the impregnating solution of cobalt precursor is continuously done and the support is strongly stirred up to guarantee the total penetration of the solution into the pore volume of the support. After the impregnation, the support is dried at temperature in the range of 100 to 250°C for a period of 18 to 24 hours.
- the impregnated support is calcined for the decomposition of cobalt (II) nitrate precursor, resulting m the formation of cobalt oxide (Co 3 0 4 ) dispersed on Nb 2 0 5 surface.
- the calcination temperature used is in the range of 300 to 600°C, preferentially b etween 350 and 550°C, and more preferentially between 400 and 500°C.
- the heating rate, during the calcination step, is an important variable, since very fast rate s may cause the creation of hot spots during the cobalt nitrate decomposition leading to the agglomeration of the metal particles.
- the agglomeration is undesirable due to the loss of metallic area, and as consequence the density of catalytic sites available for reaction significantly decreases.
- the heating rate is less than 10°C.min "1 , preferentially between 1 and 5°C.min "1 , and more preferentially between 1 and 2°C.min "1 .
- the calcination time is no less than 4 hours, preferentially between 4 and 12 hours, and more preferentially between 4 and 6 hours.
- the Nb 2 0 5 -supported cobalt catalyst is loaded to a Fischer-Tropsch synthesis reactor, where it is activated befoxe submitted to reaction mixture.
- the catalyst activation consists of the transformation of cobalt oxide into metallic cobalt by the action of a reducing gas at suitable temperature and reduction time to guarantee the complete reduction.
- the reducing gas used is hydrogen (H 2 ), carbon monoxide (CO) or mixtures thereof, but the most preferred is hydrogen. Therefore, the calcined catalyst is exposed to a hydrogen flux with a space velocity between 500 and 2,000 h "1 , preferentially between 700 and 1,500 h "1 , and more preferentially between 800 and 1,200 h "1 .
- the reduction temperature is in the range of 300 to 600°C, preferentially between 350 and 550°C, and more preferentially between 400 and 500°C.
- the reduction time should no less than 6 hours, being preferred between 10 and 24 hours and more preferred between 14 and 20 hours.
- the activation process of catalyst in hydrogen is also known as hydrogenation or reduction of the catalyst.
- the activation, reduction or hydrogenation of cobalt catalyst is the same transformation process of cobalt oxides into metallic cobalt, which is the phase that contains the active sites for FTS.
- the importance of catalyst activation goes beyond the preparation of catalytic sites of metallic character for FTS.
- the reduction is also responsible for the formation of the SMSI effect between Co and Nb 2 0 5 , which in the present invention is the essential factor to promote the activity and selectivity of the cobalt catalyst supported on niobium pentoxide.
- the temperature- programmed reduction (TPR) of the 5 wt.% Co supported on Nb 2 0 5 ( Figure 3) 94- shows that the hydrogen uptake for the complete reduction of Co species at temperatures between 370°C and 480°C is much higher than the stoichiometry.
- the hydrogen uptake excess is assigned to the partial reduction of Nb 2 0 5 to non-stoichiometric niobium oxides (NbO x ).
- NbO x non-stoichiometric niobium oxides
- These non-stoichiometric oxides are formed in the interface Co-Nb 2 0 5 , and depending upon the extent of the SMSI effect, they can partially recover the metal cobalt surface or give origin to new adsorption sites, which results in the modification of the adsorption/desorption properties of cobalt related to H 2 and CO molecules.
- the activated or reduced catalyst, loaded to a catalytic reactor for FTS, is exposed to the reaction mixture of H 2 and CO at a volumetric H 2 /CO ratio between 1 and 3, preferentially between 1.5 and 2.5, and more preferentially between 1.8 and 2.2.
- the space velocity measured as the function of the catalyst weight (WHSV: weight hourly space velocity), is in the range of 100 to 6,000 h "1 , preferentially between 300 and 2,000 h "1 , and more preferentially between 400 and 1,000 h "1 .
- the reaction temperature varies from 200 to 300°C, preferentially between 200 and 250°C, and more preferentially in the range of 210 to 240°C.
- the reaction pressure is in the range of 400 to 5,000 kPa, preferentially between 1,000 to 4,000 kPa and more preferentially between 1,800 and 2,200 kPa.
- the catalyst activity measured by the carbon monoxide conversion, and selectivity to the desirable products are function of reaction temperature and time. At low temperatures, CO conversion is lower than 40% with minimal formation ( ⁇ 5 wt.%) of carbon dioxide (C0 2 ) and methane (CH 4 ). The majority of the products are C 5 + hydrocarbons in weight amounts higher than 80 wt.%. At high temperatures, CO conversion remarkably increases reaching levels higher than 90%). However, the selectivity to light products (C0 2 , CH 4 , C 2 -C 4 ) significantly increases. Regarding the reaction time, the level of activity is low during the first hours of reaction and CO conversion gradually increases up to the steady state regime. At long periods of reaction, it is observed the formation of heavy paraffin compounds, which are hydrocarbons with carbon atoms equal or higher than 19 (Ci 9 + fraction), mainly heavy waxes.
- the cobalt catalyst supported on niobium pentoxide is highly selective to C 5 + linear paraffin with minimal formation of light products (C0 2 , CH 4 , C 2 -C 4 ), olefins, aromatics and oxygenated compounds. Moreover, the amount of hydrocarbons in the diesel oil fraction (C ⁇ 2 -C ⁇ 8 ) is very high.
- Example 1 - The preparation of 5 wt.%Co/Nb 2 0 5 catalyst
- niobium pentoxide 100 g was calcined in aerated muffle (50 ml.min "1 of dry air) at temperature of 550°C for 2 hours with the heating rate of 2°C.min "1 . After calcination, the niobium pentoxide presented a pore volume of 0.30 rnl.g "1 .
- aqueous solution of a cobalt precursor was prepared dissolving 24.7 g of cobalt (II) nitrate [Co(N0 3 ) 2 .6H 2 0] in 30 ml of distillated water. This solution was gradually added to the niobium pentoxide support, which was continuously stirred up to allow better distribution and complete penetration into the pore volume of the same. Following the impregnation, the catalyst was dried in aerated muffle at 120°C for 18 hours. The dry sample was then calcined in aerated muffle (50 ml.min "1 of dry air) at temperature of 400°C for 2 hours with a heating rate of 2°C.min "1 . The calcined catalyst has a 5 wt.% of cobalt supported on niobium pentoxide in its oxide form.
- Example 1 60 g of the catalyst prepared in the Example 1 was loaded to a fixed- bed reactor that comprises of stainless steel tube of 25.4 mm of diameter and 1 m of height. The catalyst was placed in the central part of the reactor and electrical resistance heated the catalyst region. The catalyst was then activated or reduced by passing through it pure hydrogen (1,000 ml.min "1 ) at 500°C for 16 hours at atmospheric pressure. The heating rate during the activation was of 2°C.min "1 and the space velocity around 1,000 h "1 . After activation, the temperature of the catalytic bed was then reduced under hydrogen flow to the desirable reaction temperature.
- the hydrogen flow was then adjusted to 3,900 ml.min "1 and carbon monoxide (CO) was introduced into the reactor at 1,950 ml.min "1 that results in a H 2 /CO volumetric ratio of 2.
- the space velocity, initially set at 6,000 h was gradually reduced up to 600 h "1 .
- the reactor pressure was controlled to be between 20 to 30 kPa. Table 1 shows the selectivity and product distribution for CO conversion of 30% and reaction temperature of 240°C.
- Table 1 and Table 2 show that the use of a high-surface area niobium pentoxide as a support for cobalt catalyst in Fischer-Tropsch improved the selectivity to C 5 + hydrocarbons. This fraction is richer in saturated carbon, mainly linear paraffins.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR0400086-2A BRPI0400086A (en) | 2004-03-09 | 2004-03-09 | Cobalt catalyst for fischer-tropsch synthesis, support for it, support and catalyst preparation processes and use of the catalyst |
BRPI0400086-2 | 2004-03-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005085390A1 true WO2005085390A1 (en) | 2005-09-15 |
Family
ID=34916921
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/BR2005/000028 WO2005085390A1 (en) | 2004-03-09 | 2005-03-09 | Cobalt catalyst for the synthesis of fischer-tropsch, catalyst support, processes for the preparation of support and catalyst and the use of the catalyst |
Country Status (2)
Country | Link |
---|---|
BR (1) | BRPI0400086A (en) |
WO (1) | WO2005085390A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2008714A1 (en) * | 2007-06-19 | 2008-12-31 | BASF Catalysts LLC | Process for the preparation of a cobalt-zinc oxide Fischer-Tropsch catalyst |
CN101628237B (en) * | 2008-07-16 | 2011-05-11 | 中国科学院大连化学物理研究所 | Egg-shell catalyst for preparing heavy hydrocarbon from synthesis gas, and preparation method and application thereof |
CN115501878A (en) * | 2022-09-29 | 2022-12-23 | 中国科学院青岛生物能源与过程研究所 | Method for synthesizing niobium-cobalt catalyst by in-situ centrifugation and application |
CN115739139A (en) * | 2021-09-03 | 2023-03-07 | 中国石油化工股份有限公司 | Niobium-based carrier and preparation method thereof, niobium-based supported catalyst and preparation method thereof, and monocyclic aromatic hydrocarbon production method |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4149998A (en) * | 1976-04-05 | 1979-04-17 | Exxon Research & Engineering Co. | Supported metal interaction catalysts |
US4206135A (en) * | 1979-03-12 | 1980-06-03 | Exxon Research & Engineering Co. | Catalyst comprising nickel supported on tantalum oxide or niobium oxide and their use as hydrocarbon synthesis catalysts in CO/H2 reactions |
US5472477A (en) * | 1992-05-04 | 1995-12-05 | H.C. Starck Gmbh & Co. Kg | Process for the preparation of finely divided metal and ceramic powders |
-
2004
- 2004-03-09 BR BR0400086-2A patent/BRPI0400086A/en not_active Application Discontinuation
-
2005
- 2005-03-09 WO PCT/BR2005/000028 patent/WO2005085390A1/en active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4149998A (en) * | 1976-04-05 | 1979-04-17 | Exxon Research & Engineering Co. | Supported metal interaction catalysts |
US4206135A (en) * | 1979-03-12 | 1980-06-03 | Exxon Research & Engineering Co. | Catalyst comprising nickel supported on tantalum oxide or niobium oxide and their use as hydrocarbon synthesis catalysts in CO/H2 reactions |
US5472477A (en) * | 1992-05-04 | 1995-12-05 | H.C. Starck Gmbh & Co. Kg | Process for the preparation of finely divided metal and ceramic powders |
Non-Patent Citations (3)
Title |
---|
FRYDMAN SOARES SCHMAL: "High selectivity of diesel fraction in Fischer-Tropsch synthesis with Co/Nb2O5", PROCEEDINGS OF THE 10TH INTERNATIONAL CONGRESS ON CATALYSIS, 1992, BUDAPEST, XP008037138 * |
SILVA R R C M ET AL: "EFFECT OF THE SUPPORT ON THE FISCHER-TROPSCH SYNTHESIS WITH CO/NB2O5 CATALYSTS", JOURNAL OF THE CHEMICAL SOCIETY. FARADAY TRANSACTIONS, ROYAL SOCIETY OF CHEMISTRY, CAMBRIDGE, GB, vol. 89, no. 21, 7 November 1993 (1993-11-07), pages 3975 - 3980, XP000404036, ISSN: 0956-5000 * |
SOARES R R ET AL: "Effect of preparation method on 5% Co/Nb2O5 in Fischer-Tropsch synthesis (FTS)", CATAL TODAY; CATALYSIS TODAY MAY 3 1993, vol. 16, no. 3-4, 19 November 1992 (1992-11-19), pages 361 - 370, XP008037133 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2008714A1 (en) * | 2007-06-19 | 2008-12-31 | BASF Catalysts LLC | Process for the preparation of a cobalt-zinc oxide Fischer-Tropsch catalyst |
CN101628237B (en) * | 2008-07-16 | 2011-05-11 | 中国科学院大连化学物理研究所 | Egg-shell catalyst for preparing heavy hydrocarbon from synthesis gas, and preparation method and application thereof |
CN115739139A (en) * | 2021-09-03 | 2023-03-07 | 中国石油化工股份有限公司 | Niobium-based carrier and preparation method thereof, niobium-based supported catalyst and preparation method thereof, and monocyclic aromatic hydrocarbon production method |
CN115501878A (en) * | 2022-09-29 | 2022-12-23 | 中国科学院青岛生物能源与过程研究所 | Method for synthesizing niobium-cobalt catalyst by in-situ centrifugation and application |
Also Published As
Publication number | Publication date |
---|---|
BRPI0400086A (en) | 2005-11-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Reynoso et al. | Cobalt aluminate spinel-derived catalysts for glycerol aqueous phase reforming | |
US7276540B2 (en) | Supports for high surface area catalysts | |
US7012104B2 (en) | Fischer-Tropsch processes and catalysts made from a material comprising boehmite | |
AU2006240440B2 (en) | Stabilized boehmite-derived catalyst supports, catalysts, methods of making and using | |
RU2558954C2 (en) | Producing low-molecular weight olefins from synthesis gas | |
US11278870B2 (en) | Cobalt-containing catalyst composition | |
CA2752017A1 (en) | Process for the preparation of fischer-tropsch catalysts and their use | |
CA2826520C (en) | A method of preparing a catalyst precursor | |
HAN et al. | Catalytic properties of CoAl2O4/Al2O3 supported cobalt catalysts for Fischer-Tropsch synthesis | |
JP2010532245A (en) | Production of phosphorus-containing alumina support for Fischer-Tropsch synthesis by sol-gel method and production of its catalyst | |
KR101437072B1 (en) | Catalyst for efficient co2 conversion and method for preparing thereof | |
BR112019016319A2 (en) | PROCESS TO PRODUCE A FISCHER-TROPSCH SYNTHESIS CATALYST | |
Ulfa et al. | Sequential Condensation and Hydrodeoxygenation Reaction of Furfural-Acetone Adduct over Mix Catalysts Ni/SiO 2 and Cu/SiO 2 in Water | |
WO2005085390A1 (en) | Cobalt catalyst for the synthesis of fischer-tropsch, catalyst support, processes for the preparation of support and catalyst and the use of the catalyst | |
JP2006297286A (en) | Catalyst having hetero bimodal structure | |
EA025257B1 (en) | Catalytic process for the conversion of a synthesis gas to hydrocarbons | |
AU2003297442A1 (en) | Attrition resistant bulk metal catalysts and methods of making and using same | |
WO2006093435A1 (en) | Synthesis catalyst for c5-c100 hydrocarbons and a method for producing said catalyst | |
TAKHT et al. | An egg-shell Pd-Ag/α-Al2O3 catalyst for tail-end acetylene selective hydrogenation | |
CN108187708B (en) | Phosphorus-containing high-stability heavy hydrocarbon Fischer-Tropsch synthesis catalyst and preparation method and application thereof | |
Chen et al. | The Pd/ZrO2 catalyst inversely loaded with various metal oxides for methanol synthesis from carbon dioxide | |
Reynoso Estévez et al. | Cobalt aluminate spinel-derived catalysts for glycerol aqueous phase reforming | |
JP2023554069A (en) | Fischer-Tropsch process with improved product selectivity | |
KR100897043B1 (en) | Cobalt-based catalyst for linear paraffin wax and preparing method of linear paraffin wax using them | |
Malaibari et al. | Influence of Zn and Fe Promoters on Ni-Bi/Γ-Al2o3 Catalyst for Oxidative Dehydrogenation of N-Butane to Butadiene |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DPEN | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101) | ||
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWW | Wipo information: withdrawn in national office |
Country of ref document: DE |
|
122 | Ep: pct application non-entry in european phase |