WO2009013174A2 - Method for producing olefins through reaction of carbon monoxide with hydrogen - Google Patents
Method for producing olefins through reaction of carbon monoxide with hydrogen Download PDFInfo
- Publication number
- WO2009013174A2 WO2009013174A2 PCT/EP2008/059207 EP2008059207W WO2009013174A2 WO 2009013174 A2 WO2009013174 A2 WO 2009013174A2 EP 2008059207 W EP2008059207 W EP 2008059207W WO 2009013174 A2 WO2009013174 A2 WO 2009013174A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- iron powder
- primary particles
- range
- carbonyl iron
- hydrogen
- Prior art date
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 15
- 239000001257 hydrogen Substances 0.000 title claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 239000011164 primary particle Substances 0.000 claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 41
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 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 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- 239000001569 carbon dioxide Substances 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000008188 pellet Substances 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- KZDCMKVLEYCGQX-UDPGNSCCSA-N 2-(diethylamino)ethyl 4-aminobenzoate;(2s,5r,6r)-3,3-dimethyl-7-oxo-6-[(2-phenylacetyl)amino]-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylic acid;hydrate Chemical compound O.CCN(CC)CCOC(=O)C1=CC=C(N)C=C1.N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 KZDCMKVLEYCGQX-UDPGNSCCSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/78—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 alkali- or alkaline earth metals
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- 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
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- B01J35/40—
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C07C2523/78—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 alkali- or alkaline earth metals or beryllium
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- 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
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- 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
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- 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
- C07C2523/85—Chromium, molybdenum or tungsten
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- 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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- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- C07C2531/20—Carbonyls
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
Definitions
- the present invention relates to a process for the preparation of olefins by reacting carbon monoxide with hydrogen in the presence of a ferrous heterogeneous catalyst.
- This reaction is also called Fischer-Tropsch synthesis.
- this area of product distribution can be characterized by the so-called Anderson-Schulz-Flory distribution.
- M. Janardanarao Ind. Eng. Chem. Res. 1990, 29, pages 1735-53.
- composition of the hydrocarbons formed in the Fischer-Tropsch process can be greatly influenced by the choice of catalysts used, the reactor types and the reaction conditions.
- DE-A1-28 22 656 discloses a Fischer-Tropsch process, wherein the catalyst is obtained by precipitating an organometallic iron and / or cobalt and / or nickel aggregate on an inorganic support. The precipitation of the aggregate on the carrier is effected by impregnating the carrier with a solution of the aggregate. According to this process, selective C2-C4 olefins ("light olefins”) and only small amounts of methane are formed. It is believed that the active catalyst components can be volatile under the reaction conditions, meaning metal loss, and that they are toxic.
- DE-A1-29 19 921 describes another Fischer-Tropsch process in which catalysts are used which contain polycrystalline iron whiskers as the essential catalyst component. These iron whiskers are obtained by thermal decomposition of iron pentacarbonyl in the magnetic field. The iron whiskers are preferably used as pellets. According to the teaching of this DE specification, polycrystalline whiskers are understood to mean fine iron filaments having microscopically small monocrystalline regions (page 5, 3rd paragraph). The filamentary primary particles result in shape from growth in the magnetic field. The threads have a length of z. B. 0.06 to 1 mm. The two pictures in. Expert Reports for Surface Technology, July / August 1970, page 146, show SEM images of such carbonyl iron powder with filamentary primary particles.
- the process should in particular provide as selectively as possible C2-C4-olefins (C2- to C4-olefins), in particular ethene, propene and 1-butene, with at the same time as little as possible attack of methane, carbon dioxide, alkanes (eg C2-C4-). Alkanes) and higher hydrocarbons, ie hydrocarbons with five or more carbon atoms, (C5 + fraction).
- Components of the catalyst should not be volatile under the reaction conditions. Furthermore, it should preferably not be necessary to additionally reduce or activate the catalyst before it is used.
- the proportion of spherical primary particles in the carbonyl iron powder is preferably> 90% by weight, in particular> 95% by weight, very particularly> 98% by weight.
- the spherical primary particles preferably have a diameter in the range from 0.01 to 250 ⁇ m, in particular in the range from 0.1 to 200 ⁇ m, very particularly in the range from 0.5 to 150 ⁇ m, more particularly in the range from 0.7 to 100 ⁇ m, more particularly in the range from 1 to 70 ⁇ m, particularly preferably in the range from 1.5 to 50 ⁇ m.
- the iron content of the spherical primary particles is preferably> 97% by weight, in particular> 99% by weight, in particular> 99.5% by weight, in each case calculated without any promoters present.
- the spherical primary particles are free of pores.
- the carbonyl iron powder is distinguished in particular by the fact that, in addition to the spherical primary particles, there are no filamentary primary particles, in particular those described in DE-A1-29 19 921 and .Fachberichte für heatntechnik, July / August 1970, pages 145 to 150, (see above). disclosed iron whisker containing.
- Figures 1 to 3 show SEM images of preferably used carbonyl iron powder with spherical primary particles.
- the carbonyl iron powder with spherical primary particles is obtained by thermal decomposition of gaseous iron pentacarbonyl (Fe [CO] s), which has been previously purified, in particular by distillation.
- Fe [CO] s gaseous iron pentacarbonyl
- the spherical primary particles can partially, z. B. to 25 to 95 wt .-%, be agglomerated.
- the product thus obtained is aftertreated by reduction with hydrogen.
- the carbonyl iron powder shows an advantageous catalytic effect.
- the carbonyl iron powder may be doped with one or more promoters to enhance catalytic activity.
- Promoters in iron catalysts for Fischer-Tropsch syntheses are, for. As described in M. Janardanarao, Ind. Eng. Chem. Res. 1990, 29, pages 1735 to 1753, or CD. Frohning et al. in "Chemierohstoffe from coal", 1977, pages 219-299.
- the catalysts may, for. Example, one or more of the elements vanadium, copper, nickel, cobalt, manganese, chromium, zinc, silver, gold, potassium, calcium, sodium, lithium, cesium, platinum, palladium, ruthenium, sulfur, chlorine, each in elemental form or in ionic form, contained.
- the doping of the carbonyl iron powder is in total (ie in total, if several promoters) preferably in the range of 0.01 to 30 wt .-%, particularly preferably 0.01 to 20 wt .-%, most preferably 0.1 to 15 wt .-%, z. B. 0.2 to 10 wt .-%, particularly 0.3 to 8 wt .-%, each based on iron.
- the carbonyl iron powder is doped with potassium ions and / or sodium ions as promoter.
- the carbonyl iron powder is particularly preferably doped with a total of from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, of potassium ions and / or sodium ions (in each case based on iron).
- the application of said promoters may, for. Example by impregnation of the carbonyl iron powder with aqueous salt solutions of said metals, preferably carbonates, chlorides, nitrates or oxides carried out.
- the acting as a promoter elements by thermal decomposition of the corresponding gaseous carbonyl compounds eg. As copper, cobalt or nickel carbonyls are applied during the preparation of carbonyl iron powder.
- the carbonyl iron powder may be applied to carrier materials in a further embodiment of the catalyst.
- Preferred support materials are TiO 2 , SiO 2 , Al 2 O 3 , zeolites, carbon (C).
- the optionally doped and optionally supported carbonyl iron powder can be used in the form of pellets.
- the pellets are obtained by methods known to those skilled in the art. Preferred forms of the pellets are tablets and rings.
- the pellets can also be comminuted again before use in the process according to the invention, for. B. by grinding.
- the catalysts can be converted into a synthesis-active state by treatment with hydrogen and / or carbon monoxide at elevated temperature, in particular at temperatures above 300 ° C., before they are used in the process according to the invention. However, this additional activation is not essential.
- the reactants carbon monoxide and hydrogen are preferably used in the form of synthesis gas.
- the synthesis gas can be prepared by well-known methods (such as described in Weissermel et al., Industrial Organic Chemistry, Wiley-VCH, Weinheim, 2003, pages 15 to 24), such as by reacting coal or methane with water vapor, or produced by partial oxidation of methane.
- the synthesis gas has a molar ratio of carbon monoxide to hydrogen in the range of 3: 1 to 1: 3.
- a synthesis gas is used which has a mixing molar ratio of carbon monoxide to hydrogen in the range from 2: 1 to 1: 2.
- the synthesis gas contains carbon dioxide (CO2).
- CO2 carbon dioxide
- the content of CO2 is preferably in the range of 1 to 50 wt .-%.
- the inventive process is preferably 0 to 400 C, carried out at a temperature in the range of 200 to 500 0 C, particularly 300th
- the absolute pressure is preferably in the range of 1 to 100 bar, especially 5 to 50 bar.
- the GHSV Gas Hourly Space Velocity
- the GHSV is preferably in the range of 100 to 10,000, more preferably 300 to 5000, parts by volume of feed stream per part by volume of catalyst and hour (l / l »h).
- Preferred reactors for carrying out the process according to the invention are: fluidized bed reactor, fixed bed reactor, slurry reactor.
- the catalyst is preferably used in powder form.
- the powder may be the primary particles of the carbonyl iron powder, but also agglomerations thereof.
- the powder can also be obtained by grinding previously prepared pellets.
- the catalyst is used as a shaped body, preferably in the form of pellets.
- the use of such reactors for the Fischer-Tropsch synthesis is z. B. described in CD. Frohning et al. in "Chemierharstoffe aus Kohle", 1977, pages 219-299, or BH Davis, Topics in Catalysis, 2005, 32 (3-4), pages 143-168.
- the inventive method provides a product mixture containing olefins having an olefin-carbon selectivity, in particular an ⁇ -olefin-carbon selectivity, for the C2-C4 range of preferably at least 30%, z. In the range of 30 to 45%. In the specification of selectivity, formed carbon dioxide is not considered (ie excluding CO2).
- a product mixture comprising olefins having an olefin-carbon selectivity for the C2-C4 range of at least 30%, of which at least 30% turn at least 90% ethene, Propen, 1-butene accounts ,
- formed carbon dioxide is not taken into account (i.e., excluding CO2).
- a product mixture containing olefins having an olefin-carbon selectivity for the C2-C4 range of at least 40%, z. In the range of 40 to 45%, of which at least
- olefins are z. B. used in processes for the preparation of polyolefins, epoxies, oxo products, acrylonitriles, acrolein, styrene. See also: Weisermel et al., Industrial Organic Chemistry, Wiley-VCH, Weinheim, 2003, pp. 145-192 and 267-312.
- formed carbon dioxide is not considered (i.e., without CO2).
- the product streams were heated via heated stream selectors and lines after condensing the long-chain hydrocarbons in a hot separator (160 0 C,
- Temperature program 40 ° C-5 min - 7 ° C / min - 250 ° C-5 min, carrier gas, helium.
- Carbonyl iron powder which can be used according to the invention with spherical primary particles (see also Examples 1 and 2).
Abstract
Method for producing olefins through reaction of carbon monoxide with hydrogen in the presence of an iron-containing heterogeneous catalyst, characterized in that the catalyst used comprises carbonyl iron powder with spherical primary particles.
Description
Verfahren zur Herstellung von Olefinen durch Umsetzung von Kohlenmonoxid mit Wasserstoff Process for the preparation of olefins by reaction of carbon monoxide with hydrogen
Beschreibungdescription
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Olefinen durch Umsetzung von Kohlenmonoxid mit Wasserstoff in Gegenwart eines eisenhaltigen Heterogenkatalysators.The present invention relates to a process for the preparation of olefins by reacting carbon monoxide with hydrogen in the presence of a ferrous heterogeneous catalyst.
Es ist bekannt, dass niedrigere Olefine aus Kohlenmonoxid (CO) und Wasserstoff (H2) an Metallkatalysatoren, z. B. Eisen- oder Kobalt-Katalysatoren, hergestellt werden können. Als Katalysatorvorläufer werden üblicherweise Eisenoxide eingesetzt. Solche Katalysatoren sind z. B. in US 4,544,674, US 5,100,856, US 5,1 18,715, US 5,248,701 , US 2004/0127582 A1 , H.P. Withers et al., Ind. Eng. Chem. Res. 1990, 29, Seiten 1807 bis 1814, und M.E. Dry et al., Stud. Surf. Sei. Catal., Vol. 152, 2004, Seiten 533 bis 600, beschrieben.It is known that lower olefins of carbon monoxide (CO) and hydrogen (H2) on metal catalysts, eg. As iron or cobalt catalysts can be produced. As catalyst precursors usually iron oxides are used. Such catalysts are z. In US 4,544,674, US 5,100,856, US 5,118,715, US 5,248,701, US 2004/0127582 A1, H.P. Withers et al., Ind. Eng. Chem. Res. 1990, 29, pages 1807 to 1814, and M.E. Dry et al., Stud Surf. Be. Catal., Vol. 152, 2004, pages 533-600.
Diese Umsetzung wird auch Fischer-Tropsch-Synthese genannt.This reaction is also called Fischer-Tropsch synthesis.
Herkömmliche Verfahren zur Fischer-Tropsch-Synthese produzieren Kohlenwasserstoffe in einem breiten Bereich der Produktverteilung.Conventional Fischer-Tropsch synthesis processes produce hydrocarbons in a broad range of product distribution.
Grundsätzlich kann dieser Bereich der Produktverteilung durch die sog. Anderson- Schulz-Flory-Verteilung charakterisiert werden. Vergl. auch: M. Janardanarao, Ind. Eng. Chem. Res. 1990, 29, Seiten 1735-53.Basically, this area of product distribution can be characterized by the so-called Anderson-Schulz-Flory distribution. Comp. also: M. Janardanarao, Ind. Eng. Chem. Res. 1990, 29, pages 1735-53.
Ebenso ist bekannt, dass die Zusammensetzung der beim Fischer-Tropsch-Prozess gebildeten Kohlenwasserstoffe durch die Wahl der eingesetzten Katalysatoren, der Reaktortypen und der Reaktionsbedingungen stark beeinflusst werden kann.It is also known that the composition of the hydrocarbons formed in the Fischer-Tropsch process can be greatly influenced by the choice of catalysts used, the reactor types and the reaction conditions.
Z. B. ist bekannt, dass die Produktverteilung durch Anwendung von hohen Temperaturen in Gegenwart modifizierter Eisenkatalysatoren in Richtung niedrigere Olefine verschoben werden kann: B. Büssemeier et al., Hydrocarbon Processing, Nov. 1976, Seiten 105 bis 1 12. Hauptproblem ist hier die Bildung großer Mengen an unerwünschtem Methan (CH4). Darüber hinaus sind die erforderlichen Eisenoxide als Ausgangsstoff für den Katalysator schwierig zu reduzieren.For example, it is known that the product distribution can be shifted towards lower olefins by the use of high temperatures in the presence of modified iron catalysts: B. Büssemeier et al., Hydrocarbon Processing, Nov. 1976, pages 105 to 12. The main problem here is the formation of large Amounts of undesirable methane (CH 4 ). In addition, the required iron oxides as starting material for the catalyst are difficult to reduce.
DE-A1-28 22 656 offenbart ein Fischer-Tropsch-Verfahren, wobei man den Katalysator durch Niederschlagen eines metallorganischen Eisen- und/oder Kobalt- und/oder Ni- ckel-Aggregats auf einem anorganischen Träger erhält. Das Niederschlagen des Aggregats auf dem Träger wird durch Imprägnieren des Trägers mit einer Lösung des Aggregats bewirkt. Nach diesem Verfahren sollen selektiv C2-C4-Olefine („leichte Olefine") und nur geringe Mengen an Methan entstehen. Der Hauptnachteil dieser Kataly-
satoren besteht darin, dass die aktiven Katalysatorbestandteile unter den Reaktionsbedingungen flüchtig sein können, was einen Metallverlust bedeutet, und dass sie toxisch sind.DE-A1-28 22 656 discloses a Fischer-Tropsch process, wherein the catalyst is obtained by precipitating an organometallic iron and / or cobalt and / or nickel aggregate on an inorganic support. The precipitation of the aggregate on the carrier is effected by impregnating the carrier with a solution of the aggregate. According to this process, selective C2-C4 olefins ("light olefins") and only small amounts of methane are formed. It is believed that the active catalyst components can be volatile under the reaction conditions, meaning metal loss, and that they are toxic.
DE-A1-29 19 921 beschreibt ein weiteres Fischer-Tropsch-Verfahren, in dem man Katalysatoren einsetzt, die als wesentliche Katalysatorkomponente polykristalline Ei- senwhisker enthalten. Diese Eisenwhisker werden durch thermische Zersetzung von Eisenpentacarbonyl im magnetischen Feld erhalten. Die Eisenwhisker werden bevorzugt als Pellets eingesetzt. Gemäß der Lehre dieser DE-Schrift werden unter polykri- stallinen Whiskern feine Eisenfäden mit mikroskopisch kleinen Einkristallbereichen verstanden (Seite 5, 3. Absatz). Die fadenförmigen Primärpartikel resultieren in ihrer Form aus dem Wachstum im magnetischen Feld. Die Fäden haben eine Länge von z. B. 0,06 bis 1 mm. Die beiden Bilder in .Fachberichte für Oberflächentechnik, Juli/August 1970, Seite 146, zeigen SEM-Aufnahmen von solchem Carbonyleisenpulver mit fadenförmigen Primärpartikeln.DE-A1-29 19 921 describes another Fischer-Tropsch process in which catalysts are used which contain polycrystalline iron whiskers as the essential catalyst component. These iron whiskers are obtained by thermal decomposition of iron pentacarbonyl in the magnetic field. The iron whiskers are preferably used as pellets. According to the teaching of this DE specification, polycrystalline whiskers are understood to mean fine iron filaments having microscopically small monocrystalline regions (page 5, 3rd paragraph). The filamentary primary particles result in shape from growth in the magnetic field. The threads have a length of z. B. 0.06 to 1 mm. The two pictures in. Expert Reports for Surface Technology, July / August 1970, page 146, show SEM images of such carbonyl iron powder with filamentary primary particles.
In .Fachberichte für Oberflächentechnik, Juli/August 1970, Seiten 145 bis 150, werden diese Eisenwhisker auch als Metallhaare beschrieben, die aus einem Kristallwachstum vom Metall in Fadenform, entgegen einem normalen Kristallwachstum, resultieren (Sei- te 145, 2. Absatz). In den polykristallinen Eisenwhiskern beträgt das Verhältnis von Länge zu Durchmesser z. B. > 10.In .Fachberichte fur Oberflächentechnik, July / August 1970, pages 145 to 150, these iron whiskers are also described as metal hairs resulting from crystal growth of the metal in filament form, contrary to normal crystal growth (see page 145, second paragraph). In the polycrystalline Eisenwhiskern the ratio of length to diameter z. Eg> 10.
Solche polykristallinen Eisenwhisker sind auch beschrieben in H. G. F. Wilsdorf et al., Z. Metallkde. 69 (1 1), 1978, Seiten 701 bis 705.Such polycrystalline iron whiskers are also described in H.G.F. Wilsdorf et al., Z. Metallkde. 69 (11), 1978, pages 701-705.
Der vorliegenden Erfindung lag die Aufgabe zugrunde, unter Umgehung von Nachteilen des Stands der Technik, ein verbessertes wirtschaftliches Verfahren zur Herstellung von Olefinen aufzufinden. Das Verfahren sollte insbesondere möglichst selektiv C2-C4 - Olefine (C2- bis C4 - Olefine), besonders Ethen, Propen und 1 -Buten liefern, bei gleichzeitig möglichst geringem Anfall von Methan, Kohlenstoffdioxid, Alkanen (z. B. C2-C4 - Alkanen) und höheren Kohlenwasserstoffen, also Kohlenwasserstoffen mit fünf oder mehr C-Atomen, (C5+ Fraktion). Bestandteile des Katalysators sollten unter den Reaktionsbedingungen nicht flüchtig sein. Weiterhin sollte es bevorzugt nicht notwendig sein, den Katalysator vor seinem Einsatz zusätzlich zu reduzieren bzw. zu aktivieren.It is an object of the present invention, while avoiding disadvantages of the prior art, to find an improved economical process for the production of olefins. The process should in particular provide as selectively as possible C2-C4-olefins (C2- to C4-olefins), in particular ethene, propene and 1-butene, with at the same time as little as possible attack of methane, carbon dioxide, alkanes (eg C2-C4-). Alkanes) and higher hydrocarbons, ie hydrocarbons with five or more carbon atoms, (C5 + fraction). Components of the catalyst should not be volatile under the reaction conditions. Furthermore, it should preferably not be necessary to additionally reduce or activate the catalyst before it is used.
Demgemäß wurde ein Verfahren zur Herstellung von Olefinen durch Umsetzung von Kohlenmonoxid mit Wasserstoff in Gegenwart eines eisenhaltigen Heterogenkatalysators gefunden, welches dadurch gekennzeichnet ist, dass man als Katalysator Carbonyleisenpulver mit sphärischen Primärpartikeln einsetzt.Accordingly, a process for preparing olefins by reacting carbon monoxide with hydrogen in the presence of a ferrous heterogeneous catalyst has been found, which is characterized in that the catalyst used is carbonyl iron powder having spherical primary particles.
Der Anteil an sphärischen Primärpartikeln im Carbonyleisenpulver beträgt bevorzugt > 90 Gew.-%, besonders > 95 Gew.-%, ganz besonders > 98 Gew.-%.
Die sphärischen Primärpartikel weisen bevorzugt einen Durchmesser im Bereich von 0,01 bis 250 μm, besonders im Bereich von 0,1 bis 200 μm, ganz besonders im Bereich von 0,5 bis 150 μm, weiter besonders im Bereich von 0,7 bis 100 μm, weiter besonders im Bereich von 1 bis 70 μm, besonders bevorzugt im Bereich von 1 ,5 bis 50 μm, auf.The proportion of spherical primary particles in the carbonyl iron powder is preferably> 90% by weight, in particular> 95% by weight, very particularly> 98% by weight. The spherical primary particles preferably have a diameter in the range from 0.01 to 250 μm, in particular in the range from 0.1 to 200 μm, very particularly in the range from 0.5 to 150 μm, more particularly in the range from 0.7 to 100 μm, more particularly in the range from 1 to 70 μm, particularly preferably in the range from 1.5 to 50 μm.
Der Eisengehalt der sphärischen Primärpartikel beträgt bevorzugt > 97 Gew.-%, besonders > 99 Gew.-%, insbesondere > 99,5 Gew.-%, jeweils berechnet ohne ggf. vorhandene Promotoren.The iron content of the spherical primary particles is preferably> 97% by weight, in particular> 99% by weight, in particular> 99.5% by weight, in each case calculated without any promoters present.
Bevorzugt sind die sphärischen Primärpartikel frei von Poren.Preferably, the spherical primary particles are free of pores.
Das Carbonyleisenpulver zeichnet sich im Besonderen dadurch aus, dass es neben den sphärischen Primärpartikeln keine fadenförmigen Primärpartikel, insbesondere nicht die in DE-A1-29 19 921 und .Fachberichte für Oberflächentechnik, Juli/August 1970, Seiten 145 bis 150, (siehe oben) offenbarten Eisenwhisker, enthält.The carbonyl iron powder is distinguished in particular by the fact that, in addition to the spherical primary particles, there are no filamentary primary particles, in particular those described in DE-A1-29 19 921 and .Fachberichte für Oberflächentechnik, July / August 1970, pages 145 to 150, (see above). disclosed iron whisker containing.
Die Abbildungen 1 bis 3 zeigen SEM-Aufnahmen von bevorzugt eingesetztem Carbonyleisenpulver mit sphärischen Primärpartikeln.Figures 1 to 3 show SEM images of preferably used carbonyl iron powder with spherical primary particles.
Im erfindungsgemäßen Verfahren einsetzbares Carbonyleisenpulver mit sphärischen Primärpartikeln ist z. B. unter der Bezeichnung „Carbonyleisenpulver CN" von BASF AG bzw. jetzt BASF SE, D-67056 Ludwigshafen, erhältlich.In the process according to the invention can be used carbonyl iron powder with spherical primary particles z. B. under the name "carbonyl iron powder CN" from BASF AG or now BASF SE, D-67056 Ludwigshafen, available.
Das Carbonyleisenpulver mit sphärischen Primärpartikeln wird durch thermische Zersetzung von gasförmigem Eisenpentacarbonyl (Fe[CO]s), welches besonders durch Destillation zuvor aufgereinigt wurde, erhalten.The carbonyl iron powder with spherical primary particles is obtained by thermal decomposition of gaseous iron pentacarbonyl (Fe [CO] s), which has been previously purified, in particular by distillation.
Die sphärischen Primärpartikel können teilweise, z. B. zu 25 bis 95 Gew.-%, agglome- riert sein.The spherical primary particles can partially, z. B. to 25 to 95 wt .-%, be agglomerated.
Bevorzugt wird das so erhaltene Produkt nachbehandelt durch Reduktion mit Wasserstoff.Preferably, the product thus obtained is aftertreated by reduction with hydrogen.
Bereits ohne jegliche Zusätze zeigt das Carbonyleisenpulver eine vorteilhafte katalyti- sche Wirkung.Even without any additives, the carbonyl iron powder shows an advantageous catalytic effect.
Das Carbonyleisenpulver kann zur Steigerung der katalytischen Wirkung mit einem Promotor oder mehreren Promotoren dotiert sein. Promotoren in Eisenkatalysatoren für Fischer-Tropsch-Synthesen sind z. B. beschrieben in M. Janardanarao, Ind. Eng. Chem. Res. 1990, 29, Seiten 1735 bis 1753, oder CD. Frohning et al. in „Chemierohstoffe aus Kohle", 1977, Seiten 219 bis 299.
Als geeignete Promotoren können die Katalysatoren z. B. eines oder mehrere der Elemente Vanadium, Kupfer, Nickel, Kobalt, Mangan, Chrom, Zink, Silber, Gold, Kalium, Calcium, Natrium, Lithium, Caesium, Platin, Palladium, Ruthenium, Schwefel, Chlor, jeweils in elementarer Form oder in ionischer Form, enthalten.The carbonyl iron powder may be doped with one or more promoters to enhance catalytic activity. Promoters in iron catalysts for Fischer-Tropsch syntheses are, for. As described in M. Janardanarao, Ind. Eng. Chem. Res. 1990, 29, pages 1735 to 1753, or CD. Frohning et al. in "Chemierohstoffe from coal", 1977, pages 219-299. As suitable promoters, the catalysts may, for. Example, one or more of the elements vanadium, copper, nickel, cobalt, manganese, chromium, zinc, silver, gold, potassium, calcium, sodium, lithium, cesium, platinum, palladium, ruthenium, sulfur, chlorine, each in elemental form or in ionic form, contained.
Die Dotierung des Carbonyleisenpulvers beträgt insgesamt (d.h. in Summe, wenn mehrere Promotoren) bevorzugt im Bereich von 0,01 bis 30 Gew.-%, besonders bevorzugt 0,01 bis 20 Gew.-%, ganz besonders bevorzugt 0,1 bis 15 Gew.-%, z. B. 0,2 bis 10 Gew.-%, besonders 0,3 bis 8 Gew.-%, jeweils bezogen auf Eisen.The doping of the carbonyl iron powder is in total (ie in total, if several promoters) preferably in the range of 0.01 to 30 wt .-%, particularly preferably 0.01 to 20 wt .-%, most preferably 0.1 to 15 wt .-%, z. B. 0.2 to 10 wt .-%, particularly 0.3 to 8 wt .-%, each based on iron.
In einer besonderen Ausgestaltung des erfindungsgemäßen Verfahrens ist das Carbo- nyleisenpulver mit Kaliumionen und/oder Natriumionen als Promotor dotiert.In a particular embodiment of the process according to the invention, the carbonyl iron powder is doped with potassium ions and / or sodium ions as promoter.
Besonders bevorzugt ist das Carbonyleisenpulver mit insgesamt im Bereich von 0,01 bis 10 Gew.-%, bevorzugt 0,1 bis 5 Gew.-%, an Kaliumionen und/oder Natriumionen (jeweils bezogen auf Eisen) dotiert.The carbonyl iron powder is particularly preferably doped with a total of from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, of potassium ions and / or sodium ions (in each case based on iron).
Das Aufbringen der genannten Promotoren kann z. B. durch Imprägnierung des Carbonyleisenpulvers mit wässrigen Salzlösungen der genannten Metalle, vorzugsweise Carbonaten, Chloriden, Nitraten oder Oxiden, erfolgen.The application of said promoters may, for. Example by impregnation of the carbonyl iron powder with aqueous salt solutions of said metals, preferably carbonates, chlorides, nitrates or oxides carried out.
Weiterhin können die als Promotor wirkenden Elemente durch thermische Zersetzung der entsprechenden gasförmigen Carbonylverbindungen, z. B. Kupfer-, Cobalt- oder Nickelcarbonyle, während der Carbonyleisenpulver-Herstellung aufgebracht werden.Furthermore, the acting as a promoter elements by thermal decomposition of the corresponding gaseous carbonyl compounds, eg. As copper, cobalt or nickel carbonyls are applied during the preparation of carbonyl iron powder.
Das Carbonyleisenpulver kann in einer weiteren Ausgestaltung des Katalysators auf Trägermaterialien aufgebracht sein. Bevorzugte Trägermaterialien sind TiO2, SiO2, AI2O3, Zeolite, Kohlenstoff (C).The carbonyl iron powder may be applied to carrier materials in a further embodiment of the catalyst. Preferred support materials are TiO 2 , SiO 2 , Al 2 O 3 , zeolites, carbon (C).
Im erfindungsgemäßen Verfahren kann das, ggf. dotierte und ggf. geträgerte, Carbonyleisenpulver in Form von Pellets eingesetzt werden.In the process according to the invention, the optionally doped and optionally supported carbonyl iron powder can be used in the form of pellets.
Die Pellets werden durch dem Fachmann bekannte Methoden erhalten. Bevorzugte Formen der Pellets sind Tabletten und Ringe.The pellets are obtained by methods known to those skilled in the art. Preferred forms of the pellets are tablets and rings.
Die Pellets können vor ihrem Einsatz im erfindungsgemäßen Verfahren auch wieder zerkleinert werden, z. B. durch Mahlung.The pellets can also be comminuted again before use in the process according to the invention, for. B. by grinding.
Die Katalysatoren können vor ihrem Einsatz im erfindungsgemäßen Verfahren durch Behandlung mit Wasserstoff und/oder Kohlenmonoxid bei erhöhter Temperatur, insbesondere bei Temperaturen oberhalb von 3000C, in einen syntheseaktiveren Zustand überführt werden. Diese zusätzliche Aktivierung ist jedoch nicht unbedingt erforderlich.
Im erfindungsgemäßen Verfahren werden die Edukte Kohlenmonoxid und Wasserstoff bevorzugt in Form von Synthesegas eingesetzt.The catalysts can be converted into a synthesis-active state by treatment with hydrogen and / or carbon monoxide at elevated temperature, in particular at temperatures above 300 ° C., before they are used in the process according to the invention. However, this additional activation is not essential. In the process according to the invention, the reactants carbon monoxide and hydrogen are preferably used in the form of synthesis gas.
Das Synthesegas kann nach allgemein bekannten Verfahren (wie z. B. beschrieben in Weissermel et al., Industrial Organic Chemistry, Wiley-VCH, Weinheim, 2003, Seiten 15 bis 24), wie beispielsweise durch Umsetzung von Kohle oder Methan mit Wasserdampf, oder durch partielle Oxidation von Methan hergestellt werden. Vorzugsweise weist das Synthesegas ein Molverhältnis von Kohlenmonoxid zu Wasserstoff im Bereich von 3 : 1 bis 1 : 3 auf. Besonders bevorzugt wird ein Synthesegas eingesetzt, das ein Mischungs-Molverhältnis von Kohlenmonoxid zu Wasserstoff im Bereich von 2 : 1 bis 1 : 2 aufweist.The synthesis gas can be prepared by well-known methods (such as described in Weissermel et al., Industrial Organic Chemistry, Wiley-VCH, Weinheim, 2003, pages 15 to 24), such as by reacting coal or methane with water vapor, or produced by partial oxidation of methane. Preferably, the synthesis gas has a molar ratio of carbon monoxide to hydrogen in the range of 3: 1 to 1: 3. Particularly preferably, a synthesis gas is used which has a mixing molar ratio of carbon monoxide to hydrogen in the range from 2: 1 to 1: 2.
In einer besonderen Ausführungsform des erfindungsgemäßen Verfahrens enthält das Synthesegas Kohlendioxid (CO2). Der Gehalt an CO2 liegt bevorzugt im Bereich von 1 bis 50 Gew.-%.In a particular embodiment of the process according to the invention, the synthesis gas contains carbon dioxide (CO2). The content of CO2 is preferably in the range of 1 to 50 wt .-%.
Das erfindungsgemäße Verfahren wird bevorzugt bei einer Temperatur im Bereich von 200 bis 500 0C, besonders 300 bis 400 0C, durchgeführt.The inventive process is preferably 0 to 400 C, carried out at a temperature in the range of 200 to 500 0 C, particularly 300th
Der Absolutdruck liegt bevorzugt im Bereich von 1 bis 100 bar, besonders 5 bis 50 bar.The absolute pressure is preferably in the range of 1 to 100 bar, especially 5 to 50 bar.
Die GHSV (Gas Hourly Space Velocity) liegt bevorzugt im Bereich von 100 bis 10000, besonders bevorzugt 300 bis 5000, Volumenteile Feed-Strom pro Volumenteil Katalysator und Stunde (l/l»h).The GHSV (Gas Hourly Space Velocity) is preferably in the range of 100 to 10,000, more preferably 300 to 5000, parts by volume of feed stream per part by volume of catalyst and hour (l / l »h).
Bevorzugte Reaktoren zur Durchführung des erfindungsgemäßen Verfahrens sind: Wirbelschichtreaktor, Festbettreaktor, Suspensionsreaktor.Preferred reactors for carrying out the process according to the invention are: fluidized bed reactor, fixed bed reactor, slurry reactor.
Im Wirbelschicht- und Suspensionsreaktor wird der Katalysator bevorzugt in Pulver- form eingesetzt. Das Pulver können die Primärpartikel des Carbonyleisenpulvers sein, aber auch Agglomerationen davon.In the fluidized bed and suspension reactor, the catalyst is preferably used in powder form. The powder may be the primary particles of the carbonyl iron powder, but also agglomerations thereof.
Das Pulver kann auch erhalten werden durch Mahlung von zuvor hergestellten Pellets.The powder can also be obtained by grinding previously prepared pellets.
Im Festbettreaktor wird der Katalysator als Formkörper, bevorzugt in Form von Pellets, eingesetzt.In the fixed bed reactor, the catalyst is used as a shaped body, preferably in the form of pellets.
Der Einsatz solcher Reaktoren für die Fischer-Tropsch-Synthese ist z. B. beschrieben in CD. Frohning et al. in „Chemierohstoffe aus Kohle", 1977, Seiten 219 bis 299, oder B.H. Davis, Topics in Catalysis, 2005, 32 (3-4), Seiten 143 bis 168.
Das erfindungsgemäße Verfahren liefert ein Produktgemisch enthaltend Olefine mit einer Olefin-Kohlenstoff-Selektivität, insbesondere einer α-Olefin-Kohlenstoff- Selektivität, für den C2-C4 - Bereich von bevorzugt mindestens 30 %, z. B. im Bereich von 30 bis 45 %. Bei der Selektivitätsangabe wird gebildetes Kohlendioxid nicht be- rücksichtigt (d.h. exklusive CO2).The use of such reactors for the Fischer-Tropsch synthesis is z. B. described in CD. Frohning et al. in "Chemierharstoffe aus Kohle", 1977, pages 219-299, or BH Davis, Topics in Catalysis, 2005, 32 (3-4), pages 143-168. The inventive method provides a product mixture containing olefins having an olefin-carbon selectivity, in particular an α-olefin-carbon selectivity, for the C2-C4 range of preferably at least 30%, z. In the range of 30 to 45%. In the specification of selectivity, formed carbon dioxide is not considered (ie excluding CO2).
In einer besonderen Ausführungsform erhält man ein Produktgemisch enthaltend Olefine mit einer Olefin-Kohlenstoff-Selektivität für den C2-C4 - Bereich von mindestens 30 %, wobei von diesen mindestens 30 % wiederum mindestens 90 % auf Ethen, Pro- pen, 1 -Buten entfallen. Bei der Selektivitätsangabe wird gebildetes Kohlendioxid nicht berücksichtigt (d.h. exklusive CO2).In a particular embodiment, a product mixture comprising olefins having an olefin-carbon selectivity for the C2-C4 range of at least 30%, of which at least 30% turn at least 90% ethene, Propen, 1-butene accounts , In the selectivity statement, formed carbon dioxide is not taken into account (i.e., excluding CO2).
In einer besonders bevorzugten Ausführungsform erhält man ein Produktgemisch enthaltend Olefine mit einer Olefin-Kohlenstoff-Selektivität für den C2-C4 - Bereich von mindestens 40 %, z. B. im Bereich von 40 bis 45 %, wobei von diesen mindestensIn a particularly preferred embodiment, a product mixture containing olefins having an olefin-carbon selectivity for the C2-C4 range of at least 40%, z. In the range of 40 to 45%, of which at least
40 % wiederum mindestens 90 % auf Ethen, Propen, 1 -Buten entfallen. Bei der Selektivitätsangabe wird gebildetes Kohlendioxid nicht berücksichtigt (d.h. exklusive CO2).40% turn to at least 90% ethene, propene, 1-butene. In the selectivity statement, formed carbon dioxide is not taken into account (i.e., excluding CO2).
Die erhaltenen Olefine werden z. B. in Verfahren zur Herstellung von Polyolefinen, Epoxiden, Oxoprodukten, Acrylnitrilen, Acrolein, Styrol eingesetzt. Siehe auch: Weis- sermel et al., Industrial Organic Chemistry, Wiley-VCH, Weinheim, 2003, Seiten 145 bis 192 und 267 bis 312.The obtained olefins are z. B. used in processes for the preparation of polyolefins, epoxies, oxo products, acrylonitriles, acrolein, styrene. See also: Weisermel et al., Industrial Organic Chemistry, Wiley-VCH, Weinheim, 2003, pp. 145-192 and 267-312.
BeispieleExamples
Katalysatorherstellungcatalyst Preparation
Beispiel 1 (erfindungsgemäß)Example 1 (according to the invention)
Herstellung von K-dotiertem Carbonyleisenkatalysator durch TrockenimprägnierungPreparation of K-doped carbonyl iron catalyst by dry impregnation
30 g Carbonyleisenmaterial (Carbonyleisenpulver Typ CN, BASF AG bzw. jetzt BASF SE, mit einer Korngrößenverteilung der sphärische Primärpartikel derart, dass 90 Gew.-% einen Durchmesser von kleiner 21 μm aufweisen; siehe die Abbildungen 1 bis 3) wurde unter Umgebungsbedingungen (Raumtemperatur, Normaldruck) mit 3,1 g wässriger Kaliumcarbonatlösung getränkt. Die wässrige Kaliumcarbonatlösung wurde durch Auflösen von 0,5 g Kaliumcarbonat (99 %, JT. Baker) in 2,6 g entmineralisiertem Wasser hergestellt. Der getränkte Katalysator wurde 23 h bei 1200C getrocknet. Der erhaltene Katalysator enthielt 0,6 Gew.-% K.30 g carbonyl iron material (carbonyl iron powder type CN, BASF AG or now BASF SE, with a particle size distribution of the spherical primary particles such that 90 wt .-% have a diameter of less than 21 microns, see Figures 1 to 3) was under ambient conditions (room temperature , Normal pressure) with 3.1 g of aqueous potassium carbonate solution. The aqueous potassium carbonate solution was prepared by dissolving 0.5 g of potassium carbonate (99%, JT.Baker) in 2.6 g of demineralized water. The impregnated catalyst was dried at 120 ° C. for 23 h. The resulting catalyst contained 0.6% by weight of K.
Beispiel 2 (erfindungsgemäß)Example 2 (according to the invention)
Herstellung von Na-dotiertem Carbonyleisenkatalysator durch Trockenimprägnierung
40 g Carbonyleisenmaterial (Carbonyleisenpulver Typ CN, BASF AG bzw. jetzt BASF SE, mit einer Korngrößenverteilung der sphärische Primärpartikel derart, dass 90 Gew.-% einen Durchmesser von kleiner 21 μm aufweisen; siehe die Abbildungen 1 bis 3) wurde unter Umgebungsbedingungen (Raumtemperatur, Normaldruck) mit 5,2 g wässriger Natriumcarbonatlösung getränkt. Die wässrige Natriumcarbonatlösung wurde durch Auflösen von 0,148 g Natriumcarbonat (99,5 %, Merck) in 5,0 g entminera- lisiertem Wasser hergestellt. Der getränkte Katalysator wurde 10 h bei Raumtemperatur und 20 h bei 1200C getrocknet. Der erhaltene Katalysator enthielt 0,1 Gew.-% Na.Preparation of Na-doped Carbonyl Iron Catalyst by Dry Impregnation 40 g carbonyl iron material (carbonyl iron powder type CN, BASF AG or now BASF SE, with a particle size distribution of the spherical primary particles such that 90 wt .-% have a diameter of less than 21 microns, see Figures 1 to 3) was under ambient conditions (room temperature , Normal pressure) with 5.2 g of aqueous sodium carbonate solution. The aqueous sodium carbonate solution was prepared by dissolving 0.148 g of sodium carbonate (99.5%, Merck) in 5.0 g of demineralized water. The impregnated catalyst was dried at room temperature for 10 h and at 120 ° C. for 20 h. The resulting catalyst contained 0.1 wt% Na.
Beispiel 3 (Vergleichsbeispiel)Example 3 (comparative example)
Herstellung von K-dotiertem Fe2θ3-Katalysator durch TrockenimprägnierungPreparation of K-doped Fe 2 O 3 catalyst by dry impregnation
40 g Fe2O3 (BASF AG bzw. jetzt BASF SE) wurden 8 h bei 10500C calciniert. Dann wurde das Material unter Umgebungsbedingungen (Raumtemperatur, Normaldruck) mit 1 ,9 ml wässriger Kaliumcarbonatlösung getränkt. Die wäßrige Kalium- carbonatlösung wurde durch Auflösen von 0,7 g Kaliumcarbonat (99 %, JT. Baker) in 1 ,2 g entmineralisiertem Wasser hergestellt. Der getränkte Katalysator wurde 12 h bei 120°C getrocknet und 3 h bei 5000C calciniert. Der erhaltene Katalysator enthielt 1 ,0 Gew.-% K.40 g of Fe 2 O 3 (BASF AG or now BASF SE) were calcined at 1050 ° C. for 8 hours. Then, the material was soaked under ambient conditions (room temperature, atmospheric pressure) with 1.9 ml of aqueous potassium carbonate solution. The aqueous potassium carbonate solution was prepared by dissolving 0.7 g of potassium carbonate (99%, JT.Baker) in 1.2 g of demineralized water. The impregnated catalyst was dried for 12 h at 120 ° C and calcined at 500 0 C for 3 h. The catalyst obtained contained 1.0% by weight of K.
Beispiel 4Example 4
Performance der Katalysatoren (Beispiele 1 , 2 und 3) im erfindungsgemäßen Verfahren mit vorheriger AktivierungPerformance of the catalysts (Examples 1, 2 and 3) in the process according to the invention with prior activation
Es wurde eine Reihe von vergleichenden Leistungstests mit je etwa 2,0 g Katalysator aus den Beispielen 1 , 2 und 3 und Inertmaterialverdünnung (Katalysator : Inertstoffe = 1 : 4 (Gewichtsverhältnis)) durchgeführt. Die Katalysatoren wurden in einen Festbettreaktor eingetragen und in Hb)N2 (9:1 ) (molar) 24 h bei 4800C voraktiviert. Dann wurde Synthesegas (H2:CO = 1 :1 (molar)) mit einer Rate von ungefähr 0,9 Nl/h bei 23 bar in den Reaktor eingetragen und die Temperatur auf 3400C erhöht. Als interner Standard für spätere analytische Tests wurde zusätzlich 0,1 Nl/h Stickstoffgas eingeleitet. Die Ergebnisse der über einen Zeitraum von mindestens 60 h durchgeführten Versuche sind nachstehend für die jeweiligen Katalysatorsysteme gezeigt. (Nl = Normliter = auf Normalbedingungen umgerechnetes Volumen).A series of comparative performance tests each with about 2.0 g of catalyst from Examples 1, 2 and 3 and inert dilution (catalyst: inert materials = 1: 4 (weight ratio)) was performed. The catalysts were introduced into a fixed bed reactor, and (in Hb) N 2 9: (1) molar) 24 h at 480 0 C preactivated. Then, synthesis gas (H 2 : CO = 1: 1 (molar)) was introduced at a rate of about 0.9 Nl / h at 23 bar in the reactor and the temperature increased to 340 0 C. As an internal standard for subsequent analytical tests, an additional 0.1 Nl / h of nitrogen gas was introduced. The results of the experiments carried out over a period of at least 60 hours are shown below for the respective catalyst systems. (Nl = standard liters = volume converted to standard conditions).
Performance der Katalysatoren im erfindungsgemäßen Verfahren ohne vorherige AktivierungPerformance of the catalysts in the process according to the invention without prior activation
Es wurde eine Reihe von vergleichenden Leistungstests mit je etwa 0,75 g Katalysator aus den Beispielen 1 und 3 und Inertmaterialverdünnung (Katalysator : Inertstoffe = 1 : 4 (Gewichtsverhältnis)) durchgeführt. Die Katalysatoren wurden in einen Festbettreaktor eingetragen und nicht voraktiviert. Synthesegas (HbiCO = 1 :1 (molar)) wurde mit einer Rate von ungefähr 0,5 Nl/h bei 10 bar in den Reaktor eingetragen und die Temperatur auf 3400C erhöht. Als interner Standard für spätere analytische Tests wurde zusätzlich 0,05 Nl/h Stickstoffgas eingeleitet. Die Ergebnisse der über einen Zeitraum von mindestens 80 h durchgeführten Versuche sind nachstehend für die jeweiligen Katalysatorsysteme gezeigt.A series of comparative performance tests each with about 0.75 g of catalyst from Examples 1 and 3 and inert dilution (catalyst: Inertstoffe = 1: 4 (weight ratio)) was performed. The catalysts were introduced into a fixed bed reactor and not preactivated. Synthesis gas (HbiCO = 1: 1 (molar)) was added at a rate of about 0.5 Nl / h at 10 bar in the reactor and the temperature increased to 340 0 C. As an internal standard for later analytical tests, an additional 0.05 Nl / h of nitrogen gas was introduced. The results of the experiments carried out over a period of at least 80 hours are shown below for the respective catalyst systems.
Bei den Selektivitätsangaben in den Beispielen wird gebildetes Kohlendioxid nicht berücksichtigt (d.h. ohne CO2).In the selectivity data in the examples, formed carbon dioxide is not considered (i.e., without CO2).
Zur Analytik der Reaktionsprodukte: Die Produktströme wurden über beheizte Streamselektoren und Leitungen nach Auskondensieren der langkettigen Kohlenwasserstoffe in einem Heißabscheider (1600C,For the analysis of the reaction products: The product streams were heated via heated stream selectors and lines after condensing the long-chain hydrocarbons in a hot separator (160 0 C,
25 bar) beprobt und einem online-Gaschromatograph (GC) zugeführt.25 bar) and fed to an online gas chromatograph (GC).
GC: Agilent 6890N mit FID und WLD Detektor.GC: Agilent 6890N with FID and WLD detector.
Vorsäulen: CP-Poraplot Q, Länge 12,5 m, ID 0,53 mm, Filmdicke 20 μm FID:Guard columns: CP-Poraplot Q, length 12.5 m, ID 0.53 mm, film thickness 20 μm FID:
Injektor 2500C, Splitverhältnis 50:1 , Trägergas Helium, Säule Durabond DB-1 (LängeInjector 250 0 C, split ratio 50: 1, carrier gas helium, column Durabond DB-1 (length
60 m, ID 0,32 mm, Filmdicke 3 μm), Detektor 280°C.60 m, ID 0.32 mm, film thickness 3 μm), detector 280 ° C.
WLD:WLD:
Injektor 2000C, Splitverhältnis 10:1 , Trägergas Argon, Säule Carboxen 1010 (Länge 30 m, ID 0,53 mm), Detektor 2100C.Injector 200 0 C, split ratio 10: 1 carrier gas argon column Carboxen 1010 (length 30 m, ID 0.53 mm), detector 210 0 C.
Temperaturprogramm: 40°C-5 min - 7°C/ min - 250°C-5 min, Trägergas, Helium.Temperature program: 40 ° C-5 min - 7 ° C / min - 250 ° C-5 min, carrier gas, helium.
Abbildungen 1 bis 3:Figures 1 to 3:
Erfindungsgemäß einsetzbares Carbonyleisenpulver (CEP) mit sphärischen Primärpar- tikeln (siehe auch Beispiele 1 und 2).
Carbonyl iron powder (CEP) which can be used according to the invention with spherical primary particles (see also Examples 1 and 2).
Claims
1. Verfahren zur Herstellung von Olefinen durch Umsetzung von Kohlenmonoxid mit Wasserstoff in Gegenwart eines eisenhaltigen Heterogenkatalysators, da- durch gekennzeichnet, dass man als Katalysator Carbonyleisenpulver mit sphärischen Primärpartikeln einsetzt.1. A process for the preparation of olefins by reacting carbon monoxide with hydrogen in the presence of a ferrous heterogeneous catalyst, characterized in that one uses as the catalyst carbonyl iron powder with spherical primary particles.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass die sphärischen Primärpartikel teilweise agglomeriert sind.2. The method according to claim 1, characterized in that the spherical primary particles are partially agglomerated.
3. Verfahren nach den Ansprüchen 1 oder 2, dadurch gekennzeichnet, dass die sphärischen Primärpartikel einen Durchmesser im Bereich von 0,01 bis 250 μm aufweisen.3. The method according to claims 1 or 2, characterized in that the spherical primary particles have a diameter in the range of 0.01 to 250 microns.
4. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Primärpartikel einen Eisengehalt von größer als 97 Gew.-% aufweisen, berechnet ohne Promotoren.4. The method according to any one of the preceding claims, characterized in that the primary particles have an iron content of greater than 97 wt .-%, calculated without promoters.
5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Primärpartikel porenfrei sind.5. The method according to any one of the preceding claims, characterized in that the primary particles are free of pores.
6. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Carbonyleisenpulver keine fadenförmigen Primärpartikel enthält.6. The method according to any one of the preceding claims, characterized in that the carbonyl iron powder contains no filamentary primary particles.
7. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Carbonyleisenpulver durch thermische Zersetzung von gasförmigem Eisenpentacarbonyl erhalten wurde.7. The method according to any one of the preceding claims, characterized in that the carbonyl iron powder was obtained by thermal decomposition of gaseous iron pentacarbonyl.
8. Verfahren nach dem vorhergehenden Anspruch, dadurch gekennzeichnet, dass das nach der Zersetzung von Eisenpentacarbonyl erhaltene Carbonyleisenpulver mit Wasserstoff reduziert wurde.8. Process according to the preceding claim, characterized in that the carbonyl iron powder obtained after the decomposition of iron pentacarbonyl has been reduced with hydrogen.
9. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass man die Umsetzung bei einer Temperatur im Bereich von 200 bis 500 0C durchführt.9. The method according to any one of the preceding claims, characterized in that one carries out the reaction at a temperature in the range of 200 to 500 0 C.
10. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass man die Umsetzung bei einem Absolutdruck im Bereich von 1 bis 100 bar durchführt.10. The method according to any one of the preceding claims, characterized in that one carries out the reaction at an absolute pressure in the range of 1 to 100 bar.
1 1. Verfahren nach einem der vorhergehenden Ansprüche zur Herstellung von C2- C4-Olefinen. 1 1. The method according to any one of the preceding claims for the production of C 2 -C 4 olefins.
12. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass für die Umsetzung Kohlenmonoxid und Wasserstoff im Form von Synthesegas eingesetzt werden.12. The method according to any one of the preceding claims, characterized in that carbon monoxide and hydrogen are used in the form of synthesis gas for the reaction.
13. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass Kohlenmonoxid und Wasserstoff in einem Molverhältnis im Bereich von 2 : 1 bis 1 : 2 eingesetzt werden.13. The method according to any one of the preceding claims, characterized in that carbon monoxide and hydrogen in a molar ratio in the range of 2: 1 to 1: 2 are used.
14. Verfahren nach einem der beiden vorhergehenden Ansprüche, dadurch gekenn- zeichnet, dass das Synthesegas CO2 enthält.14. The method according to any one of the preceding claims, characterized in that the synthesis gas contains CO2.
15. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Carbonyleisenpulver mit den Elementen Kalium, Vanadium, Kupfer, Nickel, Kobalt, Mangan, Chrom, Zink, Silber, Gold, Calcium, Natrium, Lithium, Cae- sium, Platin, Palladium, Ruthenium und/oder Schwefel, jeweils in elementarer15. The method according to any one of the preceding claims, characterized in that the carbonyl iron powder with the elements potassium, vanadium, copper, nickel, cobalt, manganese, chromium, zinc, silver, gold, calcium, sodium, lithium, cesium, platinum, Palladium, ruthenium and / or sulfur, each in elemental
Form oder in ionischer Form, dotiert ist.Form or in ionic form, is doped.
16. Verfahren nach dem vorhergehenden Anspruch, dadurch gekennzeichnet, dass die Dotierung des Carbonyleisenpulvers insgesamt im Bereich von 0,01 bis 30 Gew.-% (bezogen auf Eisen) beträgt.16. The method according to the preceding claim, characterized in that the doping of the carbonyl iron powder in total in the range of 0.01 to 30 wt .-% (based on iron).
17. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Carbonyleisenpulver mit insgesamt im Bereich von 0,01 bis 10 Gew.-% (bezogen auf Eisen) an Kaliumionen und/oder Natriumionen dotiert ist. 17. The method according to any one of the preceding claims, characterized in that the carbonyl iron powder with a total in the range of 0.01 to 10 wt .-% (based on iron) of potassium ions and / or sodium ions is doped.
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| EP2314557A1 (en) | 2009-10-23 | 2011-04-27 | Netherlands Organisation for Scientific Research (Advanced Chemical Technologies for Sustainability) | Production of lower olefins from synthesis gas |
| WO2011054735A1 (en) | 2009-11-06 | 2011-05-12 | Basf Se | Heterogeneous catalyst containing iron and copper and method for producing olefins by converting carbon monoxide with hydrogen |
| WO2011054738A1 (en) | 2009-11-06 | 2011-05-12 | Basf Se | Ferrous heterogeneous catalyst and method for producing olefins by converting carbon monoxide with hydrogen |
| WO2011054734A1 (en) | 2009-11-06 | 2011-05-12 | Basf Se | Heterogeneous catalyst containing iron and manganese and method for producing olefins by converting carbon monoxide with hydrogen |
| WO2011061183A1 (en) | 2009-11-19 | 2011-05-26 | Basf Se | Method for selectively producing light olefins |
| CN105582936A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Catalyst used for preparing light olefin with sintered synthetic gas, and preparation method thereof |
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| CN102639234A (en) * | 2009-11-06 | 2012-08-15 | 巴斯夫欧洲公司 | Ferrous heterogeneous catalyst and method for producing olefins by converting carbon monoxide with hydrogen |
| WO2011054738A1 (en) | 2009-11-06 | 2011-05-12 | Basf Se | Ferrous heterogeneous catalyst and method for producing olefins by converting carbon monoxide with hydrogen |
| WO2011054734A1 (en) | 2009-11-06 | 2011-05-12 | Basf Se | Heterogeneous catalyst containing iron and manganese and method for producing olefins by converting carbon monoxide with hydrogen |
| WO2011054735A1 (en) | 2009-11-06 | 2011-05-12 | Basf Se | Heterogeneous catalyst containing iron and copper and method for producing olefins by converting carbon monoxide with hydrogen |
| CN102711991A (en) * | 2009-11-06 | 2012-10-03 | 巴斯夫欧洲公司 | Heterogeneous catalyst containing iron and manganese and method for producing olefins by converting carbon monoxide with hydrogen |
| US8410018B2 (en) | 2009-11-06 | 2013-04-02 | Basf Se | Iron-comprising heterogeneous catalyst and process for preparing olefins by reaction of carbon monoxide with hydrogen |
| US8614164B2 (en) | 2009-11-06 | 2013-12-24 | Basf Se | Iron- and copper-comprising heterogeneous catalyst and process for preparing olefins by reacting carbon monoxide with hydrogen |
| US8618016B2 (en) | 2009-11-06 | 2013-12-31 | Basf Se | Iron- and manganese-comprising heterogeneous catalyst and process for preparing olefins by reacting carbon monoxide with hydrogen |
| US9156026B2 (en) | 2009-11-06 | 2015-10-13 | Basf Se | Iron-comprising heterogeneous catalyst and process for preparing olefins by reaction of carbon monoxide with hydrogen |
| WO2011061183A1 (en) | 2009-11-19 | 2011-05-26 | Basf Se | Method for selectively producing light olefins |
| US8461219B2 (en) | 2009-11-19 | 2013-06-11 | Basf Se | Process for the selective preparation of light olefins |
| CN105582936A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Catalyst used for preparing light olefin with sintered synthetic gas, and preparation method thereof |
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|---|---|
| WO2009013174A3 (en) | 2009-09-24 |
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