ZA200300334B - A reactor comprising a packed bed of supported catalyst or supported catalyst precursor, and a use of the reactor. - Google Patents
A reactor comprising a packed bed of supported catalyst or supported catalyst precursor, and a use of the reactor. Download PDFInfo
- Publication number
- ZA200300334B ZA200300334B ZA200300334A ZA200300334A ZA200300334B ZA 200300334 B ZA200300334 B ZA 200300334B ZA 200300334 A ZA200300334 A ZA 200300334A ZA 200300334 A ZA200300334 A ZA 200300334A ZA 200300334 B ZA200300334 B ZA 200300334B
- Authority
- ZA
- South Africa
- Prior art keywords
- catalyst
- reactor
- particles
- metal
- precursor
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 120
- 239000012018 catalyst precursor Substances 0.000 title claims description 25
- 239000002245 particle Substances 0.000 claims description 112
- 229910052751 metal Inorganic materials 0.000 claims description 80
- 239000002184 metal Substances 0.000 claims description 80
- 239000002243 precursor Substances 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 26
- 229930195733 hydrocarbon Natural products 0.000 claims description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- 239000004411 aluminium Substances 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 238000012856 packing Methods 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 239000011800 void material Substances 0.000 claims description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 241000264877 Hippospongia communis Species 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000006069 physical mixture Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 24
- 238000001354 calcination Methods 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 22
- 239000007789 gas Substances 0.000 description 19
- 239000002002 slurry Substances 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 239000003085 diluting agent Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000000576 coating method Methods 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- -1 alkyl acetoacetates Chemical class 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 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
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- IHEDBVUTTQXGSJ-UHFFFAOYSA-M 2-[bis(2-oxidoethyl)amino]ethanolate;titanium(4+);hydroxide Chemical compound [OH-].[Ti+4].[O-]CCN(CC[O-])CC[O-] IHEDBVUTTQXGSJ-UHFFFAOYSA-M 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical group 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 239000012685 metal catalyst precursor Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
-
- 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
- B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
- B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/34—Apparatus, reactors
- C10G2/341—Apparatus, reactors with stationary catalyst bed
-
- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00796—Details of the reactor or of the particulate material
- B01J2208/00805—Details of the particulate material
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Description
Co WO 02/07872 PCT/EP01/08019
A REACTOR COMPRISING A PACKED BED OF SUPPORTED CATALYST
OR SUPPORTED CATALYST PRECURSOR, AND A USE OF THE REACTOR
The present invention relates to a reactor comprising a packed bed of supported catalyst or supported catalyst precursor. The invention also relates to a use of the reactor, in particular the use of the reactor in a process for the preparation of hydrocarbons from synthesis gas.
The catalytic Preparation of hydrocarbons from synthesis gas, i.e. a mixture of carbon monoxide and hydrogen, is well known in the art and is commonly referred to as Fischer-Tropsch synthesis.
Catalysts suitable for use in a Fischer-Tropsch synthesis process typically contain a catalytically active metal of Group VIII of the Periodic Table of the
Elements (Handbook of Chemistry and Physics, 68th edition, CRC Press, 1987-1988) supported on a refractory oxide, such as alumina, titania, zirconia, silica or mixtures of such oxides. In particular, iron, nickel, cobalt and ruthenium are well known catalytically active metals for such catalysts. Reference may be made to EP-A-398420, EP-A-178008, EP-A~167215, EP-A-168894,
EP-A-363537, EP-A-498976 and EP-A-71770.
In the Fischer-Tropsch synthesis, as in many other chemical reactions, the Supported catalyst, the reactants and a diluent, if present, in contact with one another usually form a three phase system of gas, liquid and solid. Such three phase systems may be operated, for example, in a packed-bed reactor or in a slurry-bubble reactor. A packed-bed reactor may comprise a packed bed of solid, relatively coarse catalyst particles through which there is a flow of gas and liquid. A Slurry-bubble
Sa reactor may comprise a continuous phase of liquid with the solid, relatively fine catalyst particles suspended therein and gaseous reactants flowing as bubbles through the liquid. Traditionally, the catalytically active metal .
I) is dispersed evenly throughout the catalyst particles.
There is a continuous interest in finding catalysts a and catalyst systems for use in the Fischer-Tropsch synthesis which provide an improved activity and an improved selectivity in the conversion of carbon monoxide into valuable hydrocarbons, in particular hydrocarbons containing .5 or more carbon atoms (“Cg+ hydrocarbons” hereinafter), and which minimise the formation of methane, which is a hydrocarbon carbon frequently considered as being of lower value.
US-A-5545674 discusses the use in the Fischer-Tropsch synthesis of catalysts which have a short diffusion length, i.e. they are low in diffusion limitation. Such catalysts may have the form of a fine powder for use in a slurry-bubble reactor, or they may be in the form of so- | called shell catalysts. The shell catalysts comprise a. relatively coarse catalyst particles which contain the catalytically active metal positioned exclusively in a thin outer layer of the particles, instead of in an even distribution throughout the particles. The shell catalysts are primarily of interest for use in a packed- bed reactor. Compared with the traditional catalysts, the catalysts which have a short diffusion length exhibit a relatively high selectivity with respect to the formation of Cg+ hydrocarbons, and they suppress the production of methane.
As indicated hereinbefore, catalysts which have the form of a relatively fine powder can suitably be used in a slurry-bubble reactor. However, operational difficulties occur when the shell catalysts are used in a packed-bed reactor. Namely, given the fact that in the : shell catalysts the catalytically active metal is present only in the outer layer of the catalyst particles, the guantity of Catalytically active metal Present in the reactor is relatively low, which causes that the reactor : has a relatively low productivity, relatively to the reactor volume, when other process parameters are kept unchanged. This situation can not be improved satisfactorily by exploring the traditional catalyst shapes, such as beads or spheres, extrudates, saddles or the like. If one would choose to increase the quantity of catalytically active metal present, e.g. by decreasing the size of the catalyst particles, one would run into problems associated with a high pressure drop over the catalyst bed.
More generally, these problems occur in any chemical conversion process which involves a gas or liquid flow and in which diffusion limitation plays a role in relation to a solid catalyst. Thus, when put in a more general context, it is desirable to find a solution for the problem of using a shell catalyst in a packed-bed reactor, in an economically attractive operation.
As a solution to the stated problem, the present . invention provides a reactor comprising a packed bed of
Supported catalyst or Supported catalyst precursor wherein the supported catalyst or the supported catalyst precursor comprise an external surface comprising a catalytically active metal or a precursor compound thereof, and the packed bed has a void content of more than 50 %v and a specific surface area of more than 10 cm?/cm3, which is calculated as the total external surface area of the particles relative to the bed volume.
When operated in a chemical conversion process which involves a gas or liquid flow, a packed bed as defined ip accordance with this invention provides an improved, low pressure drop over the packed bed and an improved, high reactor productivity. In accordance with a preferred embodiment of this invention, this can be achieved by employing a packed bed of catalyst particles or catalyst precursor particles which are relatively thin and which have an extended shape, in particular particles which are "pent to some extent, such as shavings and pieces of bent wire or bent tape. The invention is preferably carried out as a fixed bed multitubular reactor.
The invention further provides the use of a reactor in accordance with this invention in a chemical conversion process, in particular a process for preparing hydrocarbons from syngas, in which the catalytically active metal is a Group VIII metal which is present at least partly in metallic form. :
The packed bed to be used in the present invention is suitably a supported catalyst in the form of a bed of solid, relatively coarse particles, or in the form of fixed structures (or arranged packings) as gauzes, corrugated sheet material which may or may not be perforated with holes, woven or non-woven structures, honeycombs and foams. For a general discussion about packed columns, especially arranged packings, reference is made toc Perry's Chemical Engineer's Handbook (1984), 50th edition, 18-19 to 18-41. The reactor is especially suitable for downward gas/liquid flow reactions.
In addition, in preferred embodiments as specified in the claims hereinafter, the invention provides a packed bed of catalyst particles or catalyst precursor : particles, a catalyst particle per se and a catalyst precursor particle per se, as well as to a packed bed comprising fixed structures or arranged packings comprising the catalyst or catalyst precursor, for example in the form of a coating and to fixed structures or arranged packings per se.
The skilled person will immediately appreciate that the invention obviates also disadvantages of a process - 5 operated in a slurry-bubble column. Namely, operation in a slurry-bubble column requires means to achieve and : maintain a homogenous distribution of the catalyst over the entire liquid volume, and there is the need of separation of the reaction product from the relatively fine catalyst powder particles.
The void content of the catalyst bed is suitably at most 95 %v, preferably at most 90 Sv. Suitably the void content is at least 55 Vv, preferably at least 60 %v, in particular at least 65 %v.
Suitably, the specific surface area of the packed bed is at least 15 cm?/cm3, more suitably at least cm? /cm3, in particular at least 25 cm?/cm3, calculated as the total external surface area of the particles relative to the bed volume. Suitably, the specific 20 surface area of the catalyst bed is at most 500 cm?/cm3, in particular at most 300 cm /cm3, on the same basis.
The specific surface area of the packed bed relates to the external, i.e. macroscopic surface area of the individual particles present in the packed bed, as opposed to their internal, i.e. microscopic surface area.
The supported catalyst may comprise particles and/or fixed structures or arranged packings. Usually the structures or packings will comprise an inert kernal (e.g. a commercially available gauze, corrugated place or (non) -woven structure) covered by a layer of catalyst or catalyst precursor. The particles may contain an inert kernal or be in the form of a homogeneous particle, i.e. the outer surface layer as well as the kernal comprising catalytically active material or precursor thereof.
:
The shape of the particles or the packings is not material to the invention, as long as = upon dumping or placing into a reactor - the particles or the packings form a packed bed in accordance with this invention. The . skilled person will appreciate that in the packed bed so formed the voids are homogeneously distributed over the : whole bed, i.e. without large empty spaces and without areas which do not have voids. For example, particles which are not free-flowing are not so easily dumped into a reactor and large empty spaces in the packed bed may result. Also particles which can easily stack are less preferred as they may cause the formation of areas which do not have voids, which leads to a higher pressure drop over the packed bed.
As indicated hereinbefore, in a preferred embodiment the packed bed comprises particles which are relatively thin and have an extended shape. In particular they are pent to some extent because this causes that the void content of the packed bed will be larger. Too much bending is less preferred and it is less preferred that the particles are branched. Namely, too much bending and branching would lead to a loss of free-flowability of the particles.
Suitably, the relatively thin and extended particles have a length, i.e. the largest dimension of the particles, of at least 1 mm, in particular at least 2 mm.
Suitably, the relatively thin and extended particles have a length of at most 50 mm, in particular at most 25 mm.
The relatively thin and extended particles may be bent and/or distorted, for example at two or more discrete ] locations, in one more directions. If the particles are bent and/or distérted, their length is deemed to be the " length of the same particles after they have been straightened out. The relatively thin and extended
CL WO 02/07872 PCT/EP01/08019 particles may have a cross-section of any shape. Typical shapes are rectangular, oval and circular.
The aspect ratio of the relatively thin and extended particles is herein defined as the ratio of their length © 5 to their quotient of the volume over the external surface area. Typically the aspect ratio is at least 10 and typically at most 1000, more preferably in the range of from 20 to 500. Independently of this criterion, the relatively thin and extended particles, whether bent or not, fit within the boundaries of a hypothetical cylinder of which the length is the length of the particles as defined hereinbefore, and of which the ratio of the length and the diameter of the circular cross-section is typically at least 2, preferably at least 3, and typically at most 100. More preferably, the ratio is in the range of from 4 to 50.
The specifications of the particles as given in the previous two paragraphs apply when all particles have the same dimensions and form. Frequently, the relatively thin and extended particles do not have the same dimensions and form, in which case it is preferred that at least 80%, in particular at least 90%, more in particular all individual particles meet the specifications as given.
The catalytically active metal or the precursor compound thereof may be evenly distributed throughout the catalyst particles. If this is the case, the void content : and the specific surface area of the packed bed as defined hereinbefore imply that the dimensions of the catalyst particles or the catalyst precursor particles are such that they exhibit the characteristics of a catalyst which has a short diffusion length.
However, preferably, the catalyst particles or the precursor catalyst particles are particles of a shell catalyst, which shell catalyst particles comprise a core and an outer layer covering the core and which outer layer comprises the metal or the precursor compound thereof. The skilled person will appreciate that the core is preferably inert, or inactive relatively to the (potential) catalytic activity of the outer layer. . - 5 Independent of whether the catalytically active metal or the precursor compound thereof is evenly distributed . throughout the catalyst particles, or the catalyst particles or the precursor catalyst particles are particles of a shell catalyst, it is preferred that the catalytically active metal or the precursor compound thereof is supported on a support.
The support is typically a material having a large internal surface area. For example, the internal surface area is at least 20 mZ2/g, especially at least 25 ml/g, and more specially at least 35 m2/g. Suitably the internal surface area is at most 400 m?/g, especially at most 200 m2/g. Preferably the internal surface area is in the range of from 40 m</g to 100 mZ2/g. The internal surface areas as quoted herein are deemed to be BET _ 20 surface areas measured in accordance with ASTM D3663-92.
The support may be for example a carbon support, but preferably it is a refractory oxide. Examples of suitable refractory oxides include silica, alumina, titania, zirconia or mixed oxides comprising silica, alumina, titania or zirconia, such as silica-alumina or physical mixtures such as a mixture of titania and silica.
Preferably, the refractory oxide comprises titania, zirconia or mixtures thereof, in particular the refractory oxide is a titania or a zirconia.
According to a preferred embodiment, the refractory oxide comprisingititania, zirconia or mixtures thereof, may further comprise up to 50 %w of another refractory oxide, typically silica or alumina, based on the total weight of the refractory oxide. More preferably, the
Co WO 02/07872 PCT/EP01/08019 additional refractory oxide, if present, comprises up to 20 %w, even more preferably up to 10 %w, on the same basis. } The refractory oxide most preferably consists of - 5 titania, in particular titania which has been prepared in the absence of sulphur-containing compounds. An example of such a preparation method involves flame hydrolysis of titanium tetrachloride.
In accordance with this invention the catalyst particles or catalyst precursor particles comprise a catalytically active metal or a precursor compound of the catalytically active metal. Typically the metal is a
Group VIII metal, as in many chemical reactions, such as
Fischer-Tropsch synthesis and hydrogenations, a Group
VIII metal catalyst may be used.
For use in the Fischer-Tropsch synthesis it is preferred that the Group VIII metal is selected from iron, nickel, cobalt and ruthenium. More preferably, cobalt or ruthenium is selected as the Group VIII metal, because cobalt based catalysts and ruthenium based catalysts give a relatively high yield of
Cs+ hydrocarbons. Most preferably, cobalt is selected as the Group VIII metal. A further metal may be present in order to improve the activity of the catalyst or the selectivity of the conversion of synthesis gas into hydrocarbons. Suitable further metals may be selected from manganese, vanadium, zirconium and rhenium. a preferred further metal is manganese or vanadium, in particular manganese.
If the catalytically active metal or the precursor compound is supported on a support, the amount of metal, in particular Group VIII metal, present on the support may vary widely. Typically, when the catalyst is used ip the Fischer-Tropsch synthesis, the amount is in the range of from 1 to 50 %w of the metal, based on the weight of the metal relative to the weight of the catalyst particles, if the metal is evenly distributed, or relative to the weight of the outer layer, if the . - 5 catalyst particles are shell catalyst particles. In accordance with the definitions given hereinbefore, the . outer layer is deemed to be the layer at the periphery of the particle which comprises 90% of the catalytically active metal or the precursor compound. Preferred ranges are from 3 to 40 %w, in particular from 5 to 30 %w, on : the same basis.
Generally, the Group VIII metal and the further metal, if present in the catalyst, are located in the catalyst particles or the catalyst precursor particles at the same locations. The atomic ratio of the Group VIII metal to the further metal is typically at least 5:1 and it is typically at most 200:1.
If a shell catalyst is used, the core comprises preferably a material with a low internal surface area, because the lower the internal surface area, the less will be the chance that the core itself exhibits catalytic activity. In accordance herewith, if the catalytically active metal or the precursor compound thereof is supported on a support, the internal surface area of the support is preferably larger than the internal surface area of the core. In general, the core will have an internal surface area of less than 20 mZ/g, especially less than 10 m?2/g and in particular less than 2 m2/g.
The core comprises frequently an inorganic material, such as a refractory oxide, a ceramic material, a metal or a carbon. Suitable refractory oxides for use as the core are silica, alumina, zirconia, magensia and titania,
and mixtures thereof Silica and alumina are a preferred refractory oxides for use as the core.
The use of a core which is based on a metal, i.e. the core is of a metallic nature, may be advantageous because - 5 it provides a shell catalyst which is strong and which has a relatively high heat conductivity. A relatively high heat conductivity is advantageous when the shell catalyst is used in a process where a substantial quantity of heat needs to be transferred from or to the reaction mixture, such as in a Fischer-Tropsch synthesis process. Suitable metals are aluminium, iron, copper, titanium and mixtures comprising one or more of these metals, like steel and brass. Aluminium and mixtures comprising aluminium are preferred, for example mixtures which comprise at least 80 sw aluminium, in particular at least 90 %$w aluminium. The latter mixtures comprise typically at most 99.9 sw aluminium, or even at most 99.99 $w aluminium. Aluminium containing mixtures may comprise from 0.01 to 5 %w of contaminants or additives selected from, for example, magnesium, silicon, copper, manganese, zinc, chromium, zirconium and titanium.
The core may be partly or wholly of a carbon or of an organic material, such as a polymer or another resinous material. Examples of suitable organic materials are polystyrenes, polyolefins, celluloses, hydrocarbon resins and epoxy resins. The carbon or the organic material may be removed in a later stage, for example during a calcination step as described hereinafter, in which case hollow catalyst particles are obtained or catalyst particles which have a core of low density (e.g. a core having a foam structure). As a matter of definition, the removal of the cere is deemed to be a replacement of the core by a core which is an empty space, and the resulting (partially) hollow catalyst particles continue to be species of a shell catalyst.
The surface of the core may be pre-treated to achieve a better adhesion of the outer layer to the core, in particular after the calcination step as described hereinafter. The surface of the core may be modified, ~ 5 e.g. by removing impurities or by covering the surface with a coating. Thus, the core may be washed with water ) or diluted acid, such as aqueous phosphoric acid; or treated with a refractory oxide sol, such as a silica sol or an alumina sol, or a paint, such as a zirconium oxide + paint. If the core comprises a refractory oxide, it may be pre-treated by calcination, for example by heating at elevated temperature, preferably at a temperature between 400 and 750 °C, more preferably between 450 and 650 °C.
The duration of the calcination is typically from 5 minutes to several hours, preferably from 15 minutes to 4 hours. Suitably, the calcination is carried out in an oxygen-containing atmosphere, preferably air.
It is not excluded that the shell metal catalyst : comprises further components, in addition to those mentioned herein. - The skilled person will be aware that suitable methods are known in the art for depositing the catalytically active metal or the precursor compound thereof on a support. For example, supported catalysts and catalyst precursors may be made by the methods known from WO-99/34917, EP-A-455307, EP-A-510771 and
EP-A-510772. These references deal with supports of titania, alumina, silica and zirconia, respectively.
The catalytically active metal and the further metal, if applicable, may be introduced onto the support in the . same manner and together. The catalytically active metal and the further metal may be introduced in the form of a precursor compound. Such precursor compounds include salts, such as nitrates, carbonates and acetates, chelates, such as acetylacetonates and alkyl acetonates,
hydroxides and oxides, and the metal itself. Generally, the calcination step, as described hereinafter, will effect that the precursor compounds of the metal will be converted into the corresponding metal oxide. } 5 The supported catalysts and catalyst precursors may be obtained in the form of a spray dried powder, or in the form of extrudates, which may be milled to obtain a powder. The powder so obtained may be mixed with a diluent to make a slurry.
In a preferred embodiment the slurry is made by admixing the catalytically active metal, optionally the further metal, and/or precursor compounds thereof, the support and/or a precursor of the support with the : diluent.
It may be advantageous to have a precursecr compound of the support present in the slurry because it increases after calcination step as described hereinafter the
Strength of the supported catalyst and/or the adhesion of the outer layer to the core, if applicable.
The precursor compound of the support may be a compound which yields a refractory oxide in the calcination step as described hereinafter. The precursor compound of the support may or may not be soluble in the diluent. The precursor compound of the support may be an organic salt or complex compound, in particular having up to 20 carbon atoms. Examples of such salts and complex compounds are salts, such as acetates, propionates, citrates; chelates, such as acetylacetonates, alkyl acetoacetates and chelates with lactic acid; alcoholates, such as ethylates, aminoethylates and isopropylates; and alkyl compounds, such as ethyl and isooctyl compounds.
Alternatively, the precursor of the support is an inorganic compound, such as a hydroxide, or an inorganic salt, such as a halide. Refractory oxide paints frequently comprise a precursor compound of a refractory oxide.
As an example, suitable precursor compounds of titanium dioxide are tetraethyl titanate, isostearoyl . titanate and octyleneglycol titanate and triethanolamine titanate. A very suitable compound, in particular for use . in combination with water as the diluent, is the ammonium salt of lactic acid chelated titanate.
The diluent for making the slurry may be an organic diluent, such as a lower alcohol, a lower ketone, a lower ester, or a lower ether, for example ethanol, acetone, methyl ethyl ketone, ethyl acetate, diethyl ether or tetrahydrofuran. In this patent document, when the term “ower” is used in conjunction with an organic compound the term specifies that the organic compound has at most six carbon atoms, in particular four carbon atoms. More suitable diluents are agueous diluents, such as a mixture of an organic diluent and water, preferably comprising at least 50 %w of water and less than 50 %w of organic diluent, based on the total weight of the diluent. Most 3 suitably, water is used as the single diluent.
The slurry may be used for spray coating onto the particles of the core, for making a shell catalyst. A suitable method and apparatus for spraying the slurry onto the particles of the core is known from Arntz et al., in “Preparation of Catalysts IV”, B Delmon et al. (BEds.), Elsevier, 1987, p. 137 ff. It is also possible to wet the particles of the core with the diluent and subsequently contacting the wetted particles with the powder, by sprinkling or dusting the powder onto the ] wetted particles or by tumbling the wetted particles in the powder.
Alternatively, the slurry may be extruded to form catalyst particles or catalyst precursor particles which do not have a core, i.e. which have the catalytically active metal or the precursor compound substantially evenly distributed over the particles. Such extruded particles with an even distribution may also be obtained : directly by the methods of W0-99/34917, EP-A-455307,
EP-A~-510771 and EP-A-510772.
In an alternative embodiment, shell catalyst may be made by surface impregnation, for example using a spraying method or an immersion method, such as disclosed in US-A-5545674, EP-A-178008 and EP-A-174696. When surface impregnation is applied, the core and the support of the outer layer are necessarily of the same material.
It is preferred that the catalyst particles or the catalyst precursor particles are subjected to a calcination step. The calcination step increases the hardness and the strength of the coating and the adhesion of the coating to the core. The calcination step involves heating at elevated temperature, preferably at a temperature between 400 and 750 °C, more preferably between 450 and 650 °C. The duration of the calcination step is typically from 5 minutes to several hours, preferably from 15 minutes to 4 hours. Suitably, the calcination step is carried out in an oxygen-containing atmosphere, preferably air.
The thickness of the outer layer of the shell catalyst particles, typically after the calcination step, is in the range of from 0.001 to 0.15 mm, preferably in the range of from 0.002 to 0.1 mm, in particular in the range of from 0.005 to 0.08 mm. The thickness of the outer layer of the shell catalyst particles is herein defined differently for the various types of shell catalyst particles. The thickness of the outer layer of a coated shell catalyst particle is defined as the quotient of the volume of the coating which contains the catalytically active metal and the external surface area of the core particle. The thickness of the outer layer of co a surface impregnated shell catalyst particle is defined as the thickness (d) of a layer at the periphery of the particle which comprises 90% of the catalytically active metal and which layer is selected such that at any point ’
I) at the inner side of the layer the shortest distance to the periphery of the particle is the same and equals d. ‘ . The thickness of the outer layer as specified in the previous paragraph applies when all particles have the same thickness of the outer layer. Frequently, the thickness of the outer layer is not the same for all : particles, in which case it is preferred that at least 80%, in particular at least 90%, more in particular all individual particles meet these specifications.
The catalytically active volume in the packed bed (i.e. the total volume of the particles which contains the catalytically active metal or the precursor compound thereof, typically after the calcination step) is suitable in the range of from 5 to 50 %v, preferably in the range of from 10 to 40 %v, relative to the volume of the packed bed. In this context, the catalytically active . : volume of a surface impregnated shell catalyst is deemed to be the volume of the layer at the periphery of the particle having the thickness d. The catalytically active volume of a coated shell catalyst particle is the volume of the coating. When the catalytically active metal or the precursor compound thereof is evenly distributed throughout the particles, the catalytically active volume is the total volume of the particles. ~
The fixed structures or arranged packings to be used in the present invention are well known in the literature . and often commercially available. These structures or packings are usually made of metals or metal alloys or in the form of ceramic foams/ceramic honeycombs. These structures or packings may be covered with a layer comprising catalytically active material or a precursor _
thereof in the way as described above. Preferred materials for the structures or packings are the same as for the shell catalyst described above.
The reactor comprises basically a vessel, which comprises appendages for feed inlet, product outlet, and internals, which can hold the packed bed in place. The reactor suitably comprises inlets and outlets for auxiliary chemicals, and means for heating and/or cooling the reactor and its contents. The reactor is suitably designed such that it withstands internal pressure. The vessel may be filled with the catalyst particles or catalyst precursor particles by dumping the particles into the vessel. A plurality of vessels may be present in the reactor, so that the reactor can hold a plurality of packed beds, for example 125000, or even up to 40000 or more. The reactor may be a multi-tubular reactor.
If desired, the calcination step may be carried out inside the reactor.
The dimensions of the packed bed may be as follows.
The height of the packed bed is typically in the range of from 1 to 20 m. The dimensions perpendicular to the height are typically in the range of from 1 cm to 10 m.
The ratio of the latter dimensions to the length of the catalyst particles is typically in the range of from 5 to 1000, preferably in the range of 7 to 500.
The reactor and the metal catalyst may be used in a process for the preparation of hydrocarbons from carbon monoxide and hydrogen. Typically, when in use in that process, the metal which is present on the catalyst is a
Group VIII metal and, typically, at least part of the
Group VIII metal is present in its metallic state.
Therefore, it is normally advantageous to activate the Group VIII metal catalyst prior to use by a reduction, in the presence of hydrogen at elevated temperature. If desired, the reduction may be carried out inside the reactor. Typically, the reduction involves treating the catalyst at a temperature in the range from 100 to 450 °C, at elevated pressure, typically from 1 to 200 bar abs, frequently for 1 to 200 hours. Pure hydrogen i may be used in the reduction, but it is usually preferred to apply a mixture of hydrogen and an inert gas, like ) nitrogen. The relative amount of hydrogen present in the mixture may range between 0.1 and 100 %v.
According to a preferred embodiment of the reduction, the catalyst is brought to the desired temperature and pressure level in a nitrogen gas atmosphere.
Subsequently, the catalyst is contacted with a gas mixture containing only a small amount of hydrogen gas, the rest being nitrogen gas. During the reduction, the relative amount of hydrogen gas in the gas mixture is gradually increased up to 50 %v or even 100 Sv.
It may be preferred to activate the Group VIII metal catalyst in-situ, that is inside the reactor for the preparation of hydrocarbons from synthesis gas.
WO-97/17137 describes an in-situ catalyst activation
B process which comprises contacting the catalyst in the presence of hydrocarbon liquid with a hydrogen-containing gas at a hydrogen partial pressure of at least 15 bar abs., preferably at least 20 bar abs., more preferably at least 30 bar abs. Typically, in this process the hydrogen partial pressure is at most 200 bar abs.
The process for the preparation of hydrocarbons from synthesis gas is typically carried out at a temperature in the range of from 125 to 350 °c, preferably from 175 to 275 °C. The pressure is typically in the range of from 5 to 150 bar abs preferably from 5 to 80 bar abs., in particular from 5 to 50 bar abs.
Hydrogen and carbon monoxide (synthesis gas) 1s typically fed to the process at a molar ratio in the range from 0.7 to 2.5. Low hydrogen to carbon monoxide molar ratios will increase the Cst+ selectivity of the catalysts, i.e. the selectivity of the formation of Cg+ hydrocarbons.
The gas hourly space velocity (“GHSV” hereinafter) may vary within wide ranges and is typically in the range from 400 to 20000 N1/1/h, more typically from 500 to 10000 N1/1/h. The term “GHSV” is well known in the art, and relates to the gas per hour space velocity, i.e. the volume of synthesis gas in N1 (i.e. at the standard temperature of 0 °C and the standard pressure of 1 bar (100,000 Pa)) which is contacted in one hour with one litre of catalyst particles, i.e. excluding inter- particular void spaces. Preferably the gas hourly space velocity is chosen in the range from 500 to 5000 N1/1/h.
The invention will now be illustrated further by means of the following Examples.
Example TI
A precursor of a shell metal catalyst was prepared as follows.
A slurry was prepared by mixing and milling together commercially available titania powder (P25 ex. Degussa,
BET surface area 50 m2/g (ASTM D3663-92)), commercially available co-precipitated cobalt/manganese hydroxide, commercially available lactic acid titanate ammonium salt (ex Dupont, available under the trademark TYZOR LA), a commercially available ceramic zirconium oxide paint (obtained from zYP Coatings, type 20) and water. The slurry contained 16 %w cobalt and 1.0 $w manganese, calculated as the weight of elemental cobalt and manganese, relatjve to the weight of the calcination residue which can be formed by drying and calcining the slurry in air at 800 °C for 2 hours.
i 20
Aluminium shavings (typical dimensions: 6 mm by 1 mm by 0.1 mm, aspect ratio about 120, bent to a curvature with 2 cm radius and distorted over up to 90 degrees) were washed with 25 %w aqueous phosphoric acid and with . water and dried. The slurry was spray-coated onto the treated aluminium shavings. The spray-coated shavings . were dried at 120 °C for 2 hours and subsequently calcined in air at 500 °C for 2 hours. The average thickness of the coating after the calcination was 30 pm.
Example IT
A precursor of a shell metal catalyst was prepared as follows.
Straight pieces of aluminium wire (length 4 mm, 0.26 mm diameter) were washed with 25 %w aqueous phosphoric acid and with water and dried. The slurry of
Example I was spray-coated onto the treated aluminium shavings. The spray-coated pieces were dried at 120 °C for 2 hours and subsequently calcined in air at 500 °C for 2 hours. The average thickness of the coating after the calcination was 30 pm. } Example TIX
Straight pieces of aluminium wire (length 4 mm, 0.5 mm diameter, dented at 1 mm intervals with 0.2 mm depth) were washed with 25 %w aqueous phosphoric acid and with water and dried.
Example IV
The uncoated aluminium shaving and pieces of wire of
Example I, II and III, and the shell metal catalyst precursors of Examples I and II were dumped in a tubular reactor having a diameter of 2.54 cm (1 inch). The void . content (in %v), the specific surface area (cm? /cm3, external surface area of the particles relative to the bed volume), the catalytically active volume (%v) of the packed beds so prepared are given in Table I. The pressure drop (bar/m bed height), measured at a nitrogen gas flow of 32.5 N1/h in model experiments using the uncoated particles, is also given in Table I.
Table I
Void Specific Catalytically | Pressure content surface .| active volume drop (3v) area ($v) (bar/m) (cm? /cm3)
Example I, 78 0.13
EH IE
Example I, 39 11
BE I
Example II, 67 51 0.18
EI I
Example II, 63 46 12 } ee] CTT
EE I A
Example V
A precursor of a shell metal catalyst was prepared as follows.
Aluminium shavings (typical dimensions 4 mm by 1 mm by 0.1 mm) were washed with 25 gw aqueous phosphoric acid, and coated with a commercially available zirconium oxide paint (obtained from ZYP Coatings, type 2Z0).
Subsequently, an aqueous slurry comprising finely dispersed commercially available cobalt hydroxide and a commercially available ammonium zirconium carbonate (MEL Chemicals, available under the trademark BACOTE 20) was spray coated onto the aluminium shavings. The slurry comprised 67 %w cobalt, calculated as the weight of cobalt metal, relative to the weight of a calcination residue which can be formed by drying and calcining the slurry in air at 800 °C for 2 hours. The spray-coated shavings were dried at 120 °C for 2 hours and subsequently calcined in air at 500 °C for 2 hours. The average thickness of the coating after the calcination was 20 um.
Example VI
The precursor shell metal catalysts prepared in
Example V was converted into an active Fisher-Tropsch catalyst by reduction, and subsequently applied in a
Fisher—-Tropsch synthesis as follows.
A micro-flow reactor containing the catalyst precursor particles in the form of a fixed bed was heated to a temperature of 280 °C, and pressurised with a continuous flow of nitrogen gas to a pressure of 1 bar abs. The catalyst precursor was reduced in-situ for 24 hours with a mixture of nitrogen and hydrogen gas.
During reduction the relative amount of hydrogen in the mixture was gradually increased from 0 %v to 100 $v. The water concentration in the off-gas was kept below 3000 ppmv.
Following reduction, the preparation of hydrocarbons } was carried out with a mixture of hydrogen and carbon monoxide at a Hp/CO ratio of 1.1:1 and a pressure of 32 par abs. The GHSV was 795 N1/1/h. The reaction temperature, expressed as the weighted average bed temperature, was 213 °C. After 40 hours of operation, the space time yield, expressed as grammes hydrocarbon product per litre catalyst particles (including the voids between the particles) per hour; the selectivity of methane, expressed in %w of the total hydrocarbon product; the selectivity to hydrocarbons containing 5 or more carbon atoms (Cs+ selectivity), expressed as %w of the total hydrocarbon product; and the selectivity of carbon dioxide, expressed in %w of the total hydrocarbon product; were as set out in Table II.
Co WO 02/07872 PCT/EP01/08019
TABLE IT
Example VII
Melt-spinned aluminium pins (length 5 mm, diameter 0.5 mm; Transmet Corporation, Columbus, Ohio, USA) were first washed with toluene and acetone. The pins were then washed with aqueous acid and with demineralized water, and dried.
A mix was made from 1827.2 g TiOy (P25 ex Degussa) with 896.7 g Co/Mn co-precipitate (molar ratio Mn/Co = 6% at/at) and water. The mix was milled for 33 minutes.
A slurry was prepared from the above mix with water and Tyzor 1A. HNO3 was added to the slurry to reduce the
PH to about 7.
A precursor shell metal catalyst was prepared by
Spraycoating the above slurry on the aforementioned pins.
The coated pins were dried at 120 °C and calcined at 500 °c.
The precursor shell metal catalyst was converted into an active Fischer-Tropsch catalyst by reduction, as described in Example VI.
Following the reduction, the catalyst was subsequently applied in a Fischer-Tropsch synthesis as follows. The preparation of hydrocarbons was carried out with a mixture of hydrogen and carbon monoxide at a Ho /CO ratio of about 1.3 and a pressure of 32 bar abs. The GHSV was 1579 N1/1/h. The reaction temperature, expressed as the weighted average bed temperature, was 227 °C. After 109 hours of operation, the space time yield, Ccg*
selectivity and the selectivity to methane and COjp, as defined in Example VI, were as listed in the following table:
Claims (10)
1. A reactor comprising a packed bed of Supported : catalyst or supported catalyst precursor wherein the supported catalyst or the supported catalyst precursor comprise an external surface comprising a catalytically © ‘active metal or a precursor compound thereof, and the packed bed has a void content of more than 50 $v and a specific surface area of more than 10 cm?/cm3, which is calculated as the total external surface area of the _ particles relative to the bed volume.
2. A reactor as claimed in claim l, characterised in that the void content of the catalyst bed is at least 60 3v, in particular at least 65 %v.
3. A reactor as claimed in claim 1 or 2, characterised in that the specific surface area of the packed bed is at least 20 cm?/cm3, in particular at least 25 cmZ/cm3, calculated as the total external surface area of the support relative to the bed volume.
4. A reactor as claimed in any of claims 1 to 3, characterised in that the packed bed comprises particles which have a length of at least 1 mm, in particular at least 2 mm, and an aspect ratio of at least 10, in particular in the range of from 20 to 500, wherein the aspect ratio is defined as the ratio of the length to the quotient of the volume over the external surface area.
5. A reactor as claimed in any of claims 1 to 3, characterised in that the packed bed comprises particles which have a length of at least 1 mm, in particular at least 2 mm, and which fit within the boundaries of a hypothetical cylinder which has a length equal to the length of the particles, and of which the ratio of the length to the diameter of the circular cross-section is at least 2, in particular at least 3, more in particular in the range of from 4 to 50.
6. A reactor as claimed in any of claims 1-5, ‘ characterised in that the total volume of the support which contains the catalytically active metal or the ‘ precursor compound thereof is in the range of from 5 to 50%, in particular in the range of from 10 to 40% of the bed volume.
7. A reactor as claimed in any of claims 1-6, characterised in that the external surface of the supported catalyst or supported catalyst precursor comprises a Group VIII metal, in particular cobalt, as the metal, supported on a (second) support which is a refractory oxide, in particular selected from silica, alumina, titania, zirconia or mixed oxides comprising silica, alumina, titania or zirconia, such as silica- alumina or physical mixtures such as a mixture of titania and silica, preferably the Group VIII metal being present at least in part in the metallic form, and the (second) : support suitably having the form of particles, extrudates or foam.
8. A reactor as claimed in any of claims 1-7, characterised in that the supported catalyst or the supported precursor catalyst are particles of a shell catalyst, which shell catalyst particles comprise a relatively inert core and an outer layer covering the core and which outer layer comprises the metal or the precursor compound, preferably the core being based on a metal, in particular selected from aluminium, iron, copper, titanium and mixtures comprising one or more of these metals, or: the catalyst being in the form of a fixed structure or arranged packing, preferably made from metal, the metal suitably having the form of gauzes, woven or non-woven structures, honeycombs or foams.
R WO 02/07872 PCT/EP01/08019
9. The use of a reactor as claimed in any of claims 1-8 in a chemical conversion process, preferably a process for preparing hydrocarbons from syngas, which process comprises contacting a mixture of carbon monoxide and 5) hydrogen in a reactor as claimed in claim 7 or 8.
10. A packed bed of supported catalyst or supported catalyst precursor as defined in claim 7 or 8, or a catalyst particle or catalyst precursor particle which forms upon dumping in a reactor together with a plurality of identical particles a packed bed as defined in claim 7 or 8.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00306331 | 2000-07-25 |
Publications (1)
Publication Number | Publication Date |
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ZA200300334B true ZA200300334B (en) | 2004-03-31 |
Family
ID=8173146
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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ZA200300334A ZA200300334B (en) | 2000-07-25 | 2003-01-13 | A reactor comprising a packed bed of supported catalyst or supported catalyst precursor, and a use of the reactor. |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP1303348A1 (en) |
AR (1) | AR029961A1 (en) |
AU (2) | AU8760301A (en) |
CA (1) | CA2416459A1 (en) |
DZ (1) | DZ3395A1 (en) |
MX (1) | MXPA03000662A (en) |
MY (1) | MY124803A (en) |
NO (1) | NO20030371L (en) |
NZ (1) | NZ523660A (en) |
RU (1) | RU2273515C2 (en) |
WO (1) | WO2002007872A1 (en) |
ZA (1) | ZA200300334B (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6451864B1 (en) * | 1999-08-17 | 2002-09-17 | Battelle Memorial Institute | Catalyst structure and method of Fischer-Tropsch synthesis |
CA2381156C (en) | 1999-08-17 | 2011-04-19 | Battelle Memorial Institute | Catalyst structure and method of fischer-tropsch synthesis |
AR061824A1 (en) | 2006-07-10 | 2008-09-24 | Shell Int Research | METHOD FOR SUPPORTING A HYDROCARBON SYNTHESIS CATALYST MATERIAL |
AU2010332961B2 (en) | 2009-12-16 | 2014-02-20 | Shell Internationale Research Maatschappij B.V. | Process for preparing a catalyst substrate from non-woven fibers |
EP2338592A1 (en) * | 2009-12-16 | 2011-06-29 | Shell Internationale Research Maatschappij B.V. | Process for manufacturing a catalyst substrate comprising non-woven fibers |
JP5615058B2 (en) * | 2010-06-29 | 2014-10-29 | バブコック日立株式会社 | Method for producing metal substrate for exhaust gas denitration catalyst |
EP2463027A1 (en) * | 2010-12-08 | 2012-06-13 | Shell Internationale Research Maatschappij B.V. | Method for the manufacture of a coated fibrous structure and a catalyst therefrom |
EP3532567B1 (en) * | 2016-10-27 | 2024-08-28 | Shell Internationale Research Maatschappij B.V. | A process for producing hydrocarbons |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3167600A (en) * | 1960-09-13 | 1965-01-26 | Robert G Worman | Packing material |
DE2818680A1 (en) * | 1978-04-27 | 1979-10-31 | Bayer Ag | PROCESS FOR PROCESSING WASTE CONTAINING NITRO-HYDROXY AROMATES |
EP0055535A1 (en) * | 1980-12-31 | 1982-07-07 | Imperial Chemical Industries Plc | Fluid purification |
EP0082614B1 (en) * | 1981-12-21 | 1986-07-23 | Imperial Chemical Industries Plc | Process for steam reforming a hydrocarbon feedstock and catalyst therefor |
JPH084749B2 (en) * | 1985-01-21 | 1996-01-24 | 日本碍子株式会社 | Ceramic honeycomb structure |
DK156701C (en) * | 1987-08-27 | 1990-01-29 | Haldor Topsoe As | PROCEDURE FOR IMPLEMENTING Heterogeneous CATALYTIC CHEMICAL REACTIONS |
NL1006477C2 (en) * | 1997-07-04 | 1999-01-05 | Gastec Nv | Reactor and method for carrying out a chemical reaction. |
US6302188B1 (en) * | 1998-04-28 | 2001-10-16 | Megtec Systems, Inc. | Multi-layer heat exchange bed containing structured media and randomly packed media |
-
2001
- 2001-07-11 CA CA002416459A patent/CA2416459A1/en not_active Abandoned
- 2001-07-11 RU RU2003105239/12A patent/RU2273515C2/en not_active IP Right Cessation
- 2001-07-11 AU AU8760301A patent/AU8760301A/en active Pending
- 2001-07-11 DZ DZ013395A patent/DZ3395A1/en active
- 2001-07-11 MX MXPA03000662A patent/MXPA03000662A/en unknown
- 2001-07-11 EP EP01967153A patent/EP1303348A1/en not_active Withdrawn
- 2001-07-11 AU AU2001287603A patent/AU2001287603B2/en not_active Ceased
- 2001-07-11 NZ NZ523660A patent/NZ523660A/en unknown
- 2001-07-11 WO PCT/EP2001/008019 patent/WO2002007872A1/en active IP Right Grant
- 2001-07-23 MY MYPI20013460 patent/MY124803A/en unknown
- 2001-07-23 AR ARP010103503A patent/AR029961A1/en not_active Application Discontinuation
-
2003
- 2003-01-13 ZA ZA200300334A patent/ZA200300334B/en unknown
- 2003-01-24 NO NO20030371A patent/NO20030371L/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
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MXPA03000662A (en) | 2003-10-15 |
AR029961A1 (en) | 2003-07-23 |
WO2002007872A1 (en) | 2002-01-31 |
NO20030371L (en) | 2003-03-20 |
NZ523660A (en) | 2004-07-30 |
AU8760301A (en) | 2002-02-05 |
DZ3395A1 (en) | 2002-01-31 |
RU2273515C2 (en) | 2006-04-10 |
AU2001287603B2 (en) | 2004-11-25 |
NO20030371D0 (en) | 2003-01-24 |
EP1303348A1 (en) | 2003-04-23 |
MY124803A (en) | 2006-07-31 |
CA2416459A1 (en) | 2002-01-31 |
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