EP2872599A1 - Procédé de production d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et un catalyseur utilisable dans le procédé - Google Patents
Procédé de production d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et un catalyseur utilisable dans le procédéInfo
- Publication number
- EP2872599A1 EP2872599A1 EP13735333.0A EP13735333A EP2872599A1 EP 2872599 A1 EP2872599 A1 EP 2872599A1 EP 13735333 A EP13735333 A EP 13735333A EP 2872599 A1 EP2872599 A1 EP 2872599A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- hydrocarbons
- carbon dioxide
- magnesium
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 249
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 104
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 70
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 67
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 61
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 60
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 40
- 239000001257 hydrogen Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title abstract description 16
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 99
- 229910052700 potassium Inorganic materials 0.000 claims description 59
- 239000011591 potassium Substances 0.000 claims description 55
- 239000010949 copper Substances 0.000 claims description 53
- 229910052742 iron Inorganic materials 0.000 claims description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 43
- 229910052802 copper Inorganic materials 0.000 claims description 43
- 239000011777 magnesium Substances 0.000 claims description 38
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 37
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 37
- 229910052749 magnesium Inorganic materials 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 37
- 239000011701 zinc Substances 0.000 claims description 36
- 229910052726 zirconium Inorganic materials 0.000 claims description 34
- 239000011572 manganese Substances 0.000 claims description 33
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 32
- 229910052725 zinc Inorganic materials 0.000 claims description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052748 manganese Inorganic materials 0.000 claims description 29
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 28
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 22
- 229910052746 lanthanum Inorganic materials 0.000 claims description 21
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 150000001336 alkenes Chemical class 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- 229910052707 ruthenium Inorganic materials 0.000 claims description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 150000001340 alkali metals Chemical class 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- -1 ethylene, propylene Chemical group 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 5
- 239000003350 kerosene Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 description 52
- 239000002184 metal Substances 0.000 description 52
- 150000002739 metals Chemical class 0.000 description 46
- 239000000243 solution Substances 0.000 description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 26
- 239000007789 gas Substances 0.000 description 23
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 20
- 229910010413 TiO 2 Inorganic materials 0.000 description 18
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 238000005984 hydrogenation reaction Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000011363 dried mixture Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 description 4
- 229960001545 hydrotalcite Drugs 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 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 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Chemical class CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical class CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical class CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- 229910002552 Fe K Inorganic materials 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical class CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical class CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical class CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical class CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 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
- B01J23/70—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
- B01J23/78—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- 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
- B01J23/72—Copper
-
- 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
-
- 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
- B01J23/80—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 zinc, cadmium or mercury
-
- 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
- B01J23/83—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 rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0242—Coating followed by impregnation
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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
- 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
- B01J37/031—Precipitation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
Definitions
- the present invention relates to a method for
- Presence of a specific catalyst is implemented. With the method according to the invention can be used as fuels
- Hydrocarbons are formed with very high selectivity. Furthermore arise in the process with good
- CO2 carbon dioxide
- global warming global warming
- CO2 is suitable here as the carbon source, since CO 2 is consumed in the production and only the previously bound amount CO 2 is released when the recovered fuel is combusted.
- RWGS reverse water-gas shift
- the RWGS or their reverse reaction is a
- polymer production In addition to fuel production, the largest consumer of fossil carbon carriers in the chemical industry is polymer production.
- polymer production predominantly short-chain olefins (ethylene, propylene, butenes) are used as starting materials, from which, directly or after modification, polymers, such as
- Polyethylene, polypropylene, polyacrylates and polyurethanes are produced mainly from fossil raw materials in refineries by steaming. Other methods, like the
- CO2 must be stored in underground caverns. However, the CO2 could react with the rock and endanger the stability of the caverns.
- Iron catalysts which can contain cerium as a promoter were described in S.-S. Nam et al. , J. Chem. Res. (1999) 344 and S.- S. Nam et al. , Appl. Catal. A 179 (1999) 155
- the object of the invention is a process for producing hydrocarbons and a catalyst therefor
- Hydrocarbons in particular the chain lengths C5-C15 but also the chain lengths C2-C4 at the highest possible conversion of C0 2 already without recycling of excess CO2 is achieved.
- a method is sought with which a higher selectivity for liquid C5-C15
- Hydrocarbons for example, are suitable as fuels, and a higher CC> 2 conversion than with the
- Catalysts of the prior art for example the 100Fe6, 6Cul5, 7A14K from S.-R. Yan et al. in Appl. Catal. A 194-195 (2000) 63-70.
- Catalyst contains iron and at least one alkali metal and further satisfies at least one of the following features (i) to (iii):
- the catalyst contains, based on the
- Total weight of the catalyst iron in an amount of at least 10% by weight, preferably from 15 to 35% by weight, and further copper and at least one other selected from magnesium, zinc, lanthanum and zirconium;
- the catalyst comprises TiO 2 and / or a
- the catalyst further contains ruthenium and / or cobalt.
- the metals such as iron, alkali metal (eg lithium, sodium and potassium), copper, magnesium, zinc, lanthanum, aluminum, zirconium, manganese, ruthenium and cobalt can also be used as compounds, in particular as Oxides are present.
- the metals Preferably, at least a portion of the metals, more preferably all metals are present as an oxide.
- Hydrocarbons of carbon dioxide and hydrogen wherein the carbon dioxide is reacted with hydrogen in the presence of a catalyst, wherein the catalyst contains iron and at least one alkali metal.
- the at least one alkali metal is advantageously selected from the group consisting of lithium, sodium, potassium and rubidium.
- the catalyst contains potassium as the at least one alkali metal.
- the proportion of the at least one alkali metal is 1-30 wt .-% and particularly preferably 5-12 wt .-% with respect to the iron content in
- the potassium content is preferably 1 to 30 wt .-% and particularly preferably 5 to 12 wt .-% with respect to the iron content in the catalyst.
- the catalyst comprises 1O2 and / or a
- the catalyst further contains ruthenium and / or cobalt.
- the at least one alkali metal contained in the catalyst of process (i) is potassium.
- the catalyst of process (i) may be two further representatives selected from magnesium, zinc, lanthanum and
- the catalyst of process (i) may also contain manganese and / or aluminum.
- the catalyst of process (i) may include manganese and copper.
- the catalyst contains:
- Potassium, zirconium and manganese are:
- a promoter is defined as a constituent or component of a catalyst which positively influences the catalytic reaction.
- the weight ratio of iron to the total weight of all promoters in the catalyst of process (i) is preferably between 1.5 and 15.
- the catalyst of process (i) additionally contains ruthenium.
- the components iron and ruthenium are active components.
- an active component is defined as the catalytically active ingredient or component.
- the catalyst of process (i) can be a
- Catalyst support comprises (unsupported catalyst), the total weight of all promoters in the catalyst based on the catalyst as a whole preferably between 15 and 50 wt .-% and particularly preferably between 30 and 40 wt .-%.
- Particularly preferred examples of the unsupported catalyst of process (i) are:
- the metals may be present as oxide and the proportions of the metals in wt .-%, based on the total weight of all metals in metallic form in the catalyst are given.
- the metals Preferably, at least a portion of the metals, more preferably all metals are present as an oxide.
- the catalyst support may be selected from the group consisting of Al 2 O 3, Al 2 O 3 MgO, TiC> 2, La 2 O 3, ZrC> 2, ZrC> 2 La 2 C> 3, ZrO 2, SiO 2, zeolites and aluminum -Magnesiumhydroxycarbonaten be selected.
- AI2O3-MgO refers to mixtures of Al2O3 and MgO, the
- ZrC> 2-1 ⁇ 203 refers to mixtures of ZrÜ2 and La2Ü3, wherein the mixing ratio can be arbitrary, preferably the weight ratio of La 2 0 3 : Zr0 2 is between 5:95 and 15:85.
- Zr0 2 -Si0 2 denotes mixtures of ZrC> 2 and S1O2, where the
- the weight ratio between Al 2 O 3 and MgO may be arbitrary.
- the weight ratio of Al 2 O 3: MgO is between 30:70 (e.g., Pural MG70) and 50:50.
- Magnesium hydroxycarbonates include amorphous and crystalline forms, among the crystalline forms is hydrotalcite
- Preferred catalyst supports are 102, Al 2 O 3 and aluminum magnesium hydroxycarbonate, with T1O 2 being particularly preferred.
- the support materials Al2O3 and T1O2 are advantageous in terms of the yield of C5-C15 hydrocarbons. If 1O2 is used as catalyst support in the catalyst of process (i), a high yield of C5-C15
- the catalyst support preferably has a particle size of 100 to 250 pm.
- Process (i) is preferably between 1.5 and 20
- the supported catalyst of process (i) is
- catalysts 0.07RuI, 27MgI, 78Cu 20Fe 1.74K / Al 2 O 3 ;
- the metals may be present as oxide and the proportions of the metals in wt .-%, based on the sum of
- Catalyst and the catalyst support are specified.
- At least a portion of the metals, more preferably all metals are present as an oxide.
- Another embodiment of the process according to the invention relates to the use of a catalyst which satisfies feature (ii) (process (ii)). If Ti0 2 or aluminum magnesium hydroxycarbonates are used as catalyst carriers in the catalyst of the process according to the invention, a particularly high yield of valuable metal is obtained
- Hydrocarbons such as C 2 -C 4 and C 5 -C 15 hydrocarbons, achieved while at the same time little undesirable methane is formed.
- the catalyst supports TiC> 2 and aluminum magnesium hydroxycarbonates preferably have a particle size of 100 to 250 pm.
- Total catalyst is preferably between 10 and 50 wt .-% iron, more preferably between 15 and 35 wt .-% iron and most preferably between 20 and 25 wt .-% iron. Due to this high iron content, a particularly high CC> 2 conversion is achieved.
- the catalyst in process (ii) contains potassium as the at least one alkali metal.
- the catalyst comprises at least one further member selected from the group consisting of magnesium, zinc, lanthanum, aluminum, zirconium, manganese and copper.
- the at least one further representative is magnesium, zinc or copper.
- the catalyst in process (ii) contains potassium and copper and at least one further representative selected from the group consisting of aluminum,
- Embodiments of process (ii) include
- the components potassium, copper, magnesium, zinc, lanthanum, zirconium, manganese and aluminum are promoters.
- the weight ratio of iron to the total weight of all promoters in the catalyst of process (ii) is the weight ratio of iron to the total weight of all promoters in the catalyst of process (ii)
- Process (ii) is preferably between 1.5 and 20% by weight and more preferably between 3 and 10% by weight, based on the weight of the catalyst as a whole.
- the catalyst of process (ii) additionally contains ruthenium.
- the components iron and ruthenium are active components.
- metals may be present as oxide and the proportions of the metals in wt .-%, based on the sum of Total weight of all metals in metallic form in
- Catalyst and the catalyst support are specified.
- At least a portion of the metals, more preferably all metals are present as an oxide.
- a further embodiment of the process according to the invention relates to the use of a catalyst which satisfies feature (iii) (process (iii)).
- the components are iron, ruthenium and cobalt
- the catalyst of process (iii) contains potassium as the at least one alkali metal.
- the catalyst contains at least one further representative, this being selected from the group consisting of magnesium, zinc, lanthanum,
- Aluminum, zirconium, manganese and copper is selected.
- the at least one further representative is magnesium, zinc or copper.
- the catalyst in process (iii) contains potassium and copper and at least one further member selected from the group
- the catalyst comprises:
- the components potassium, copper, magnesium, zinc, lanthanum, zirconium, manganese and aluminum are promoters.
- the weight ratio of iron to the total weight of all promoters in the catalyst of process (iii) is
- the catalyst in process (iii) may be both supported and unsupported.
- the total weight of all promoters in the catalyst relative to the catalyst as a whole is preferably between 15 and 50% by weight and more preferably between 30 and 40% by weight.
- the catalyst support may be selected from the group consisting of Al 2 O 3 , Al 2 O 3 MgO, TiO 2 , La 2 O 3 , ZrO 2 , ZrO 2 La 20 3 , Zr0 2 -Si0 2 , zeolites and aluminum magnesium hydroxycarbonates be selected.
- AI2O3-MgO refers to mixtures of Al2O3 and MgO, the
- Mixing ratio can be arbitrary.
- r02-La2Ü3 denotes mixtures of ZrC> 2 and L .203, wherein the mixing ratio can be arbitrary, preferably the weight ratio of La 2 0 3 : Zr0 2 is between 5:95 and 15:85.
- Zr0 2 -Si0 2 denotes mixtures of Zr02 and SXO2, where the
- the weight ratio of Al 2 O 3: MgO is between 30:70 (e.g., Pural MG70) and 50:50.
- Magnesium hydroxycarbonates include amorphous and crystalline forms, among the crystalline forms is hydrotalcite
- Preferred catalyst supports are iO 2, Al 2 O 3 and aluminum magnesium hydroxycarbonate, with 10O 2 being particularly preferred. These support materials are with regard to the yield of C5- C ] _5 hydrocarbons advantageous.
- the catalyst support preferably has a particle size of 100 to 250 ⁇ .
- Process (iii) is preferably between 1.5 and 20% by weight and more preferably between 3 and 10% by weight, based on the weight of the catalyst as a whole.
- Catalyst and the catalyst support are specified.
- At least a portion of the metals, more preferably all metals are present as an oxide.
- process (iv) relates to the preparation of
- Hydrocarbons of carbon dioxide and hydrogen wherein the carbon dioxide is reacted with hydrogen in the presence of a catalyst, wherein the catalyst contains iron, potassium, copper and magnesium, wherein iron in an amount of
- At least 8 wt .-% preferably between 10 and 50 wt .-%, particularly preferably between 15 and 35 wt .-%, based on the total weight of the catalyst is included.
- Catalyst may also contain manganese.
- the proportion of potassium is 1-30 wt .-% and particularly preferably 5-12 wt .-% with respect to the iron content in the catalyst.
- the components potassium, copper, magnesium, and manganese are promoters.
- Iron is an active component
- the weight ratio of iron to the total weight of all promoters in the catalyst of the process is preferably between 1.5 and 15.
- the catalyst of the process may comprise a catalyst support on which the active components and promoters
- the total weight of all promoters in the catalyst based on the catalyst as a whole is preferably between 15 and 50% by weight and
- the catalyst support can be selected from the group consisting of Al 2 O 3, Al 2 O 3 -MgO, TiC> 2, I 2 O 3, ZrC> 2, ZrC 1 -Cl 2, ZrO 2-SiC> 2, zeolites and Aluminum magnesium hydroxycarbonates be selected.
- AI2O3-MgO refers to mixtures of Al2O3 and MgO, the
- Zr02-La2Ü3 denotes mixtures of ZrC> 2 and L .203, wherein the mixing ratio can be arbitrary, preferably the weight ratio of La2Ü3: ZrC> 2 is between 5:95 and 15:85.
- Zr0 2 -SiC> 2 denotes mixtures of ZrC > 2 and S1O2, where the
- the weight ratio of Al 2 O 3: MgO is between 30:70 (e.g., Pural MG70) and 50:50.
- Magnesium hydroxycarbonates include amorphous and crystalline forms, among the crystalline forms is hydrotalcite
- the catalyst support is preferably Al 2 O 3.
- Catalyst support preferably has a particle size of 100 to 250] i.
- Method is preferably between 1.5 and 20 wt .-% and particularly preferably between 3 and 10 wt .-% based on the weight of the catalyst as a whole.
- the following catalysts are particularly preferred: 10El, 0Mg 2.0Cu 0.8K / A1 2 0 3
- Catalyst and the catalyst support are specified.
- At least a portion of the metals, more preferably all metals are present as an oxide.
- Another aspect of the invention relates to the use of the catalysts as described above in the process according to the invention, as described, for example, in the attached US Pat
- Claim 1 is defined.
- the process of the invention relates to the reaction of carbon dioxide with hydrogen in the presence of a catalyst, i. the hydrogenation of carbon dioxide by hydrogen in the presence of a catalyst
- the RWGS reaction of carbon dioxide to carbon monoxide takes place and the carbon monoxide formed is converted to hydrocarbons in a Fischer-Tropsch synthesis.
- the process of the invention may also be referred to generally as a Fischer-Tropsch process. Preferred are the
- Hydrocarbons C5-C15 hydrocarbons and / or C2-C4 hydrocarbons.
- the reaction of the carbon dioxide with hydrogen in the process of the invention preferably takes place at a temperature of 150 to 400 ° C, more preferably 300 to 370 ° C, even more preferably 320 ° C to 370 ° C and most preferably 350 ° C , A temperature of 150 to 400 ° C leads to a particularly high yield
- Hydrocarbons especially C5-C15 hydrocarbons.
- a temperature of 300 ° C to 350 ° C is particularly suitable in relation to the yield of C5-C15 hydrocarbons.
- Hydrogen at a pressure of 10 to 50 bar and more preferably between 15 to 30 bar instead.
- the reaction of the carbon dioxide is carried out with hydrogen at a temperature of 300 ° C and a pressure of 15 bar or at a temperature of 350 ° C and a pressure of 10 bar.
- the carbon dioxide used in the process according to the invention can be obtained by flue gas separation from the exhaust gas of power plants, which preferably generate electrical energy from fossil fuels.
- the hydrogen gas used in the process according to the invention can by
- Hydrocarbons from carbon dioxide and hydrogen can be carried out in a fixed bed, fluidized bed or bubble column reactor.
- suitable fixed bed reactors are gas-flow fixed bed catalytic reactors,
- Bubble column reactors and tube bundle reactors. in the A gas-flow catalytic fixed bed reactor according to the invention is preferably used.
- Hydrogen, water, unreacted carbon dioxide, and carbon monoxide may contain.
- the carbon monoxide is
- the product mixture contains C5-C15 and C2-C hydrocarbons. Contain the C2-C4
- Hydrocarbons C2-C alkanes so they can be dehydrogenated after their separation to C2-C alkenes, especially ethylene, propylene and butenes.
- c 5 c ⁇ 15 hydrocarbons include linear, branched and cyclic alkanes and alkenes with a chain length of 5 to 15 carbon atoms.
- Examples of the C5-C15 alkanes are linear, branched and cyclic isomers of pentanes, hexanes, heptanes, octanes, nonanes, decanes, undecans, dodecanes, tridecanes, tetradecanes and pentadecanes.
- Examples of the 05-015 alkenes include linear, branched and cyclic isomers of pentenes, hexenes, heptenes, octenes, nonenes, decenes, undecenes, dodecenes, tridecenes,
- the C5-C15 hydrocarbons are preferably linear and / or branched alkanes and alkenes.
- C2-C4 hydrocarbons include C2-C4 alkanes and C2-C4 alkenes containing from 2 to 4 carbon atoms, where the C4 alkanes and C4 alkenes can be both linear and branched.
- Examples of the C 2 -C 4 hydrocarbons are ethane, ethylene, propane, propylene, n-butane, isobutane, 1-butene, 2-butene and 2-methyl-1-propene.
- Butenes include n-butane, isobutane, 1-butene, 2-butene and 2-methyl-1-propene.
- the hydrocarbons produced are preferably predominantly C 2 -C 15 hydrocarbons, ie those produced
- Hydrocarbons include C2-C15 hydrocarbons in an amount of at least 50 mol%.
- the hydrocarbons of the product mixture obtained in the process according to the invention are preferably ⁇ 50 mol%, more preferably ⁇ 70 mol% of C2-C15 hydrocarbons, based on the hydrocarbons produced.
- Hydrocarbons which are useful, for example, as fuels such as gasoline, diesel and kerosene
- C2-C hydrocarbons which may be after dehydration as
- the molar ratio of c is 5 ⁇ 15 c hydrocarbons to C2-C4 hydrocarbons in the product mixture preferably>. 1
- methane and higher hydrocarbons (with more than 16
- the product gas is preferably cooled in a phase separator to 35 ° C, thereby to deposit water in liquid form. If necessary, excess carbon dioxide can be removed from the product gas by absorption in a further step.
- the product gas can be passed through a medium, for example a solvent, which
- the separated carbon dioxide gas may include the educt gas stream comprising hydrogen gas and carbon dioxide gas in the
- the product gas can be separated in a cryogenic separation apparatus or by cryogenic separation technique into those components which are liquid or gaseous at room temperature (20 ° C), with a cryogenic heat exchanger being preferred.
- a cryogenic separation apparatus or by cryogenic separation technique into those components which are liquid or gaseous at room temperature (20 ° C), with a cryogenic heat exchanger being preferred.
- the C5-C15 As liquids, the C5-C15
- Hydrocarbons, methane, excess carbon monoxide and hydrogen are obtained in gaseous form.
- excess hydrogen gas can be recycled by removing methane from the gas mixture of methane, excess carbon monoxide, and hydrogen by means of membrane separation technology or cryogenic separation.
- the recycled hydrogen gas can then be recycled to the educt gas stream of the process according to the invention
- the catalyst is reduced with hydrogen before use in the process according to the invention.
- the catalyst is, for example, at 500 ° C in a
- Inert gas stream e.g., nitrogen
- hydrogen e.g., hydrogen
- the catalyst used in the process of the present invention can be prepared by precipitation from metal salt solutions or by milling metal oxides. This gives an unsupported catalyst.
- supported catalyst can be prepared by reacting a catalyst support with metal salt solutions, e.g. aqueous metal nitrate solutions, impregnated, for example
- the impregnated catalyst support is dried after each impregnation step.
- the catalysts become oxalate during production
- oxalate is preferably in the form of
- Ammonium oxalate or metal oxalate is added. Particularly preferred is ammonium oxalate. As has been shown, this leads to a better distribution of the active components, in particular iron, and the promoters in the catalyst or on the support.
- impregnated catalyst supports are preferably calcined after drying. Calcination may be carried out, for example, in a muffle furnace in still air (e.g., at 350 ° C) or in the inert gas stream (e.g., at 400 ° C). When a catalyst containing oxalate is calcined, complete decomposition (combustion) of the oxalate occurs; the oxalate is removed without residue during calcination.
- the invention relates to the
- Catalyst as such.
- the catalyst according to the invention comprises as
- Catalyst components based on the total weight of the catalyst, at least 10 wt .-%, preferably 10-50 wt .-%, particularly preferably 15 and 35 wt .-% and very particularly preferably 20-25 wt .-% iron, and potassium, Copper and at least one other component selected from magnesium, zinc, lanthanum and zirconium.
- the catalyst at least 10 wt .-%, preferably 10-50 wt .-%, particularly preferably 15 and 35 wt .-% and very particularly preferably 20-25 wt .-% iron, and potassium, Copper and at least one other component selected from magnesium, zinc, lanthanum and zirconium.
- the catalyst based on the total weight of the catalyst, at least 10 wt .-%, preferably 10-50 wt .-%, particularly preferably 15 and 35 wt .-% and very particularly preferably 20-25 wt .-% iron, and potassium, Copper and at least one other component selected from
- catalyst according to the invention at least one of the following metals: manganese, ruthenium, aluminum and cobalt.
- Preferred embodiments of the catalyst according to the invention contain
- the components iron and ruthenium are active components.
- Magnesium, zinc, lanthanum, aluminum, zirconium and manganese in the catalyst according to the invention is preferably between 1.5 and 15.
- at least some of the metals are present, more preferably all metals are present as oxide.
- the catalyst according to the invention can be both supported and unsupported.
- the total weight of all metals selected from the group consisting of potassium, copper, magnesium, zinc, lanthanum, aluminum, zirconium and manganese in the catalyst based on the total catalyst is preferably between 15 and 50 wt .-% and especially
- unsupported catalyst of the invention preferably between 30 and 40 wt .-%.
- Particularly preferred examples of the unsupported catalyst of the invention are: H, 3Lal4, 1Cu70.7 Fe3.9K; and
- the metals may be present as oxide and the proportions of the metals in wt .-%, based on the total weight of all metals in metallic form in the catalyst are given.
- the support may be selected from the group consisting of Al 2 O 3 , Al 2 O 3 MgO, TiO 2 , La 2 O 3 , ZrO 2 , ZrO 2 -LaO 3 / ZrO 2 -SiO 2 , zeolites and aluminum magnesium hydroxycarbonates be.
- AI2O3-MgO refers to mixtures of Al2O3 and MgO, the
- Zr02-La2Ü3 denotes mixtures of ZrC> 2 and La2Ü3, wherein the mixing ratio can be arbitrary, preferably the weight ratio of La 2 0 3 : ZrC> 2 is between 5:95 and 15:85.
- Zr0 2 -Si0 2 denotes mixtures of ZrO 2 and S1O2, where the
- the weight ratio of Al 2 O 3: MgO is between 30:70 (e.g., Pural MG70) and 50:50.
- Magnesium hydroxycarbonates include amorphous and crystalline forms, among the crystalline forms is hydrotalcite
- Preferred catalyst supports are TiO 2 ; AI2O3 and aluminum magnesium hydroxycarbonate. These support materials are advantageous in terms of the yield of C5-C15 hydrocarbons. Contains the catalyst T1O2 as a carrier, so is a high yield of C5-C15 hydrocarbons in the
- Copper, magnesium, zinc, lanthanum, aluminum, zirconium and manganese in the supported catalyst is preferably between 1.5 and 20 wt .-% and particularly preferably between 3 and 10 wt .-% based on the weight of the catalyst as a whole.
- the supported catalyst of the invention is preferably selected from the following catalysts:
- the metals may be present as oxide and the proportions of the metals in wt .-%, based on the sum of
- Catalyst and the carrier are specified.
- at least a portion of the metals, more preferably all metals are present as an oxide.
- Another aspect of the invention relates to the use of the catalysts, as described above, in one of
- Catalyst 2 II, 6Mg II, 6Mn II, 6Cu 58.2Fe 7, OK
- Catalyst 2 was prepared analogously to the preparation of catalyst 1 from 2.45 g of Mg (NO 3 ) 2 '6H 2 O, 1.06 g of Mn (NO 3 ) 2 .4 ⁇ 2 0, 0.88 g of Cu (NO 3 ) 2 -3H 2 0, 7.81 g Fe (NO 3 ) 3 .9H 2 0 and 0.36 g K 0 3
- Step 1 5 ml of an aqueous Fe (NO 3 ) 3 solution (content 48.7 g / 1 Fe) were added to lg Ti0 2 (Degussa Aerolyst 7708, particle size 0.1-0, 25 mm) while shaking at room temperature.
- aqueous Fe (NO 3 ) 3 solution content 48.7 g / 1 Fe
- Step 2 5 ml of an aqueous KNO 3 solution (content 3.69 g / 1 K) were pipetted onto the dried mixture from step 1 with shaking at room temperature, the mixture was heated to 100 ° C. and concentrated by shaking at 100 ° C. and dried , Step 3: To the dried mixture of Step 2 was added 5 ml of an aqueous under stirring at room temperature
- Step 4 The dried mixture was calcined for 5 hours in a muffle furnace at 350 ° C in air.
- Catalyst 4 was prepared analogously to the preparation of catalyst 3, wherein in step 2, the content of the aqueous K O3 solution was 4.85 g / 1 K.
- Catalyst 5 0, lRu 0.2Cu 0.3Zn 19.2Fe 1.3K / TiO;
- Catalyst 5 was prepared analogously to the preparation of catalyst 3, wherein in step 1, the content of the aqueous
- step 4 the content of the aqueous K O 3 solution was 3.41 g / 1 K
- step 3 the content of the aqueous Zn (NO 3) 2 solution 0.71 g / 1 Zn, and step 4 was replaced by the following steps 4 through 6:
- Step 4 To the dried mixture of step 3, shaking at room temperature 5 ml of an aqueous
- Step 5 To the dried mixture from step 4, shaking at room temperature, 5 ml of an aqueous
- Step 6 The dried mixture was calcined for 5 hours in a muffle furnace at 350 ° C in air.
- Catalyst 6 0.07Ru 0.3Zn 19.2Fe 2, OK / Tip
- Catalyst 6 was prepared analogously to the preparation of catalyst 3, wherein in step 1, the content of the aqueous
- step 4 the content of the aqueous KNO 3 solution was 5.13 g / 1 K
- step 3 the content of the aqueous Zn (NO 3) 2 solution was 0 , 73 g / 1 Zn
- step 4 was replaced by the following steps 4 and 5:
- Step 4 To the dried mixture of step 3, shaking at room temperature 5 ml of an aqueous
- Step 5 The dried mixture was calcined for 5 hours in a muffle furnace at 350 ° C in air.
- Catalyst 7 2.2Zr l, 7Mn 2.4Zn 18.8Fe 1.6K / TiO ?
- Catalyst 7 was prepared analogously to the preparation of catalyst 5, wherein in step 1 the content of the aqueous Fe (NO 3) 3 solution was 51.3 g / 1 Fe, in step 2 the content of the aqueous KNO 3 solution was 4.37 g / 1 K in step 3, the content of the aqueous n (NO 3) 2 solution was 6.68 g / 1 Zn, in step 4, the content of the aqueous ZrO (NO 3) 2 solution was 5.91 g / 1 Zr and in step 5, the content of the aqueous Mn (NC> 3) 2 solution was 4.62 g / 1 Mn.
- Catalyst 8 0.97Cu 19.16Fe 1.63K / Tip ?
- Catalyst 8 was prepared analogously to the preparation of catalyst 3, wherein in step 1 5 ml of an aqueous solution of Fe (NC> 3) 3 (content 49.1 g / 1 Fe) and 2 ml of a
- Ammonium oxalate solution (content 25.15 g / 1 oxalate) were used, in step 2 the content of the aqueous KNO3 solution was 4.17 g / 1 K and in step 3 the content of the aqueous Cu (N0 3 ) 2 solution 2, 48 g / 1 Cu.
- Catalyst 9 was prepared analogously to the preparation of catalyst 6, wherein in step 1 the content of the aqueous Fe (NO 3) 3 solution was 51.2 g / 1 Fe, in step 2 the content of the aqueous KNO 3 solution was 4.42 g / 1K, in Step 3, the content of the Cu (NO3) 2 aqueous solution was 10.24 g / 1Cu, and in Step 4, the content of the ZrO (NO3) 2 aqueous solution was 5.71 g / 1Zr.
- Catalyst 10 3, lZr 2, 8Mn 0.9Cu 18.8Fe 1.4K / Tip ?
- Catalyst 10 was prepared analogously to the preparation of catalyst 5, wherein in step 1 the content of the aqueous Fe (NO 3) 3 solution was 51.5 g / 1 Fe, in step 2 the content of the aqueous KNC> 3 solution was 3.80 g / 1 K was, in step 3, the content of the aqueous ZrO (NO 3) 2 solution was 8.43 g / 1 Zr, in step 4, the content of the aqueous Mn (NO 3) 2 solution was 7.62 g / 1 Mn and in step 5, the content of the aqueous Cu (NC> 3) 2 solution was 2.57 g / l Cu.
- Hydrogen was carried out in a fixed bed reactor (stainless steel tube, Inner diameter 5 mm). All catalysts were used in a grain fraction of 100-250 ⁇ m to
- the analysis of the product gas was carried out by an on-line coupled Gas Chromatograph in the gas phase. For this purpose, an operating pressure of 10 bar was chosen and, secondly, all the pipes and valves after the reactor and the GC inlet system were heated to at least 150 ° C. In addition, a hot gas separator (150 ° C) and a cold gas separator (room temperature), each with integrated aerosol filter, were integrated into the flue pipe. It became the two-dimensional
- thermal conductivity detector CO2, ethylene, ethane, water, H2, N2, methane, CO
- FID Flame ionization detector
- Gas chromatographs were equipped with a PorapakQ column and a PoraPlotQ column. The columns were heated with a temperature program from the start temperature 50 ° C to 200 ° C.
- the second channel was equipped with a FFAP column and an Al203 / KCl column (25m x 0.32mm, 5pm film thickness) with the FFAP column operating at a temperature of 50-200 ° C.
- the A ⁇ Oß / KCl column was washed with a
- Olefin content proportion of C2-C4 olefins in mol% based on all the C2-C4 hydrocarbons (Y (C 2 -C 4))
- the catalysts 11-67 were prepared by impregnation of carrier materials. If several components are contained on a carrier, the impregnation became sequential,
- Aerolyst 7708 Aerolyst 7708), S1O2 (Degussa Aerolyst 355), aluminum magnesium hydroxycarbonate with a weight ratio A1 2 0 3 : MgO of 30: 70 (Pural MG70)
- Table 2 summarizes the compositions of catalysts 11-67. The proportion of the respective metal in metallic form is given in wt .-% and refers to the total weight of all metals in metallic form in the catalyst and the catalyst support. Table 2: Compositions of the catalysts
- Oxalate was used in the preparation of the catalyst, but in the composition of the calcined catalyst, oxalate is not included.
- Oxalate was used in the preparation of the catalyst, but in the composition of the calcined catalyst, oxalate is not included.
- Oxalate was used in the preparation of the catalyst, but in the composition of the calcined catalyst, oxalate is not included.
- Oxalate was used in the preparation of the catalyst, but in the composition of the calcined catalyst, oxalate is not included.
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Abstract
L'invention concerne un procédé de production d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène selon lequel on fait réagir le dioxyde de carbone avec l'hydrogène en présence d'un catalyseur spécial. Le procédé selon l'invention permet de former comme carburants (essence, diesel, kérosène) d'intéressants hydrocarbures C5-C15 avec une sélectivité très élevée. Des hydrocarbures C2-C4 qui peuvent être utilisés comme substances de départ de valeur dans l'industrie chimique se forment dans le procédé avec une bonne sélectivité. Dans le procédé, on obtient déjà une conversion élevée de CO2 sans recyclage de dioxyde de carbone excédentaire. L'invention concerne, selon un autre aspect, les catalyseurs proprement dits.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP13735333.0A EP2872599A1 (fr) | 2012-07-13 | 2013-07-12 | Procédé de production d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et un catalyseur utilisable dans le procédé |
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Application Number | Priority Date | Filing Date | Title |
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EP12176417.9A EP2684936A1 (fr) | 2012-07-13 | 2012-07-13 | Procédure de fabrication d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et d'un catalyseur utilisable dans le procédé |
EP13735333.0A EP2872599A1 (fr) | 2012-07-13 | 2013-07-12 | Procédé de production d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et un catalyseur utilisable dans le procédé |
PCT/EP2013/064806 WO2014009534A1 (fr) | 2012-07-13 | 2013-07-12 | Procédé de production d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et un catalyseur utilisable dans le procédé |
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EP2872599A1 true EP2872599A1 (fr) | 2015-05-20 |
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EP12176417.9A Withdrawn EP2684936A1 (fr) | 2012-07-13 | 2012-07-13 | Procédure de fabrication d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et d'un catalyseur utilisable dans le procédé |
EP13735333.0A Withdrawn EP2872599A1 (fr) | 2012-07-13 | 2013-07-12 | Procédé de production d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et un catalyseur utilisable dans le procédé |
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EP12176417.9A Withdrawn EP2684936A1 (fr) | 2012-07-13 | 2012-07-13 | Procédure de fabrication d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et d'un catalyseur utilisable dans le procédé |
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US (1) | US20150197462A1 (fr) |
EP (2) | EP2684936A1 (fr) |
WO (1) | WO2014009534A1 (fr) |
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WO2019123251A1 (fr) * | 2017-12-18 | 2019-06-27 | King Abdullah University Of Science And Technology | Catalyseurs pour l'hydrogénation du co2 |
FI128568B (en) * | 2018-06-11 | 2020-08-14 | Teknologian Tutkimuskeskus Vtt Oy | Method and apparatus for the formation and use of hydrocarbons |
CN113117683A (zh) * | 2021-04-16 | 2021-07-16 | 郑州大学 | 负载型催化剂及其制备方法 |
CN113797955B (zh) * | 2021-10-25 | 2023-04-04 | 中国华能集团清洁能源技术研究院有限公司 | 一种二氧化碳加氢制低碳烯烃的催化剂及其制备方法 |
JP2024075191A (ja) * | 2022-11-22 | 2024-06-03 | 本田技研工業株式会社 | 二酸化炭素還元触媒装置、二酸化炭素還元方法、及び触媒の製造方法 |
CN117019151B (zh) * | 2023-07-05 | 2024-04-12 | 珠海市福沺能源科技有限公司 | 一种二氧化碳加氢的空腔微球催化剂及其制备方法和应用 |
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KR100351625B1 (ko) * | 1999-11-11 | 2002-09-11 | 한국화학연구원 | 탄화수소 제조용 촉매 |
CN1159098C (zh) * | 2001-07-12 | 2004-07-28 | 中国科学院山西煤炭化学研究所 | 一种费托合成用铁基催化剂及其制备方法 |
CN101293206B (zh) * | 2008-04-21 | 2010-09-22 | 神华集团有限责任公司 | 一种费托合成用铁基催化剂及其制备方法 |
US8658554B2 (en) * | 2009-11-04 | 2014-02-25 | The United States Of America, As Represented By The Secretary Of The Navy | Catalytic support for use in carbon dioxide hydrogenation reactions |
-
2012
- 2012-07-13 EP EP12176417.9A patent/EP2684936A1/fr not_active Withdrawn
-
2013
- 2013-07-12 EP EP13735333.0A patent/EP2872599A1/fr not_active Withdrawn
- 2013-07-12 US US14/414,601 patent/US20150197462A1/en not_active Abandoned
- 2013-07-12 WO PCT/EP2013/064806 patent/WO2014009534A1/fr active Application Filing
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US20150197462A1 (en) | 2015-07-16 |
EP2684936A1 (fr) | 2014-01-15 |
WO2014009534A1 (fr) | 2014-01-16 |
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