EP2162210A2 - Synthetic methods for liquid hydrocarbons from syngas over alumina-silica based catalysts and preparation methods thereof - Google Patents
Synthetic methods for liquid hydrocarbons from syngas over alumina-silica based catalysts and preparation methods thereofInfo
- Publication number
- EP2162210A2 EP2162210A2 EP08705004A EP08705004A EP2162210A2 EP 2162210 A2 EP2162210 A2 EP 2162210A2 EP 08705004 A EP08705004 A EP 08705004A EP 08705004 A EP08705004 A EP 08705004A EP 2162210 A2 EP2162210 A2 EP 2162210A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- alumina
- support
- silica
- catalyst
- pores
- 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- Withdrawn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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 239000003054 catalyst Substances 0.000 title claims abstract description 114
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 108
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 20
- 239000007788 liquid Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims description 20
- 238000010189 synthetic method Methods 0.000 title description 2
- 239000011148 porous material Substances 0.000 claims abstract description 141
- 238000006243 chemical reaction Methods 0.000 claims abstract description 90
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 66
- 230000002902 bimodal effect Effects 0.000 claims abstract description 28
- 229910017052 cobalt Inorganic materials 0.000 claims description 47
- 239000010941 cobalt Substances 0.000 claims description 47
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 47
- 239000000741 silica gel Substances 0.000 claims description 27
- 229910002027 silica gel Inorganic materials 0.000 claims description 27
- 229910052707 ruthenium Inorganic materials 0.000 claims description 26
- 229910052681 coesite Inorganic materials 0.000 claims description 23
- 229910052906 cristobalite Inorganic materials 0.000 claims description 23
- 229910052682 stishovite Inorganic materials 0.000 claims description 23
- 229910052905 tridymite Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910001593 boehmite Inorganic materials 0.000 claims description 19
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 19
- 229910001868 water Inorganic materials 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- -1 aluminum alkoxide Chemical class 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052702 rhenium Inorganic materials 0.000 claims description 5
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 35
- 229910052726 zirconium Inorganic materials 0.000 description 27
- 239000000047 product Substances 0.000 description 25
- 230000007423 decrease Effects 0.000 description 24
- 230000008569 process Effects 0.000 description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 239000006185 dispersion Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000002243 precursor Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000009257 reactivity Effects 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 230000001603 reducing effect Effects 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000012546 transfer Methods 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 230000007774 longterm Effects 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- 229910007928 ZrCl2 Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000635 electron micrograph Methods 0.000 description 5
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000002779 inactivation Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910021091 Co(NO3)26H2O Inorganic materials 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 238000010744 Boudouard reaction Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000005937 allylation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000012686 silicon precursor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229940032094 squalane Drugs 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/69—Pore distribution bimodal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/8913—Cobalt and noble metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J37/033—Using Hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- B01J23/8896—Rhenium
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- B01J37/0201—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
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
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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
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
Definitions
- the present invention relates to an alumina- silica support having a double-layered, bimodal pore structure with different pore sizes in which alumina is dispersed on silica surface, a catalyst using the support and a method for preparing liquid hydrocarbons in high yield by Fischer-Tropsch reaction of a syngas (CO/H 2 /CO 2 ) in the presence of the catalyst.
- the GTL process has been refined and adjusted continuously.
- the GTL technology based on the F-T synthesis not only improves the environmental problem at the gas field, but also enables the production of clean synthetic fuels through processing of the flared gas.
- the GTL products which are clean liquid fuels with little sulfur, may provide a better market value than the conventional petroleum products produced by refining a crude oil. For instance, in 2004, Europe, Japan, etc., reduced the sulfur content in the diesel oil for cars from 500 ppm to 50 ppm and they are expected to further lower to below 10 ppm in the near future.
- the F-T synthetic oil is a fuel that can effectively cope with the recently reinforced environmental regulations from developed countries, along with the recent regulations of the Kyoto Protocol. According to Sasol's LCA study, the with little sulfur and aromatic compounds, the GTL synthetic fuel gives off less exhaust gas and nitrogen oxides and is capable of reducing the atmospheric acidification by more than 40 %. Further, the emission of particulate matters (PM) can be reduced by more than 40 % and the utilization of F-T synthetic oil in cars is expected to reduce the emission of greenhouse gas by at least 12 % through increased thermal efficiency.
- PM particulate matters
- the F-T synthesis originates from the preparation of synthetic fuel from syngas by coal gasification invented by German chemists Fischer and Tropsch in 1923.
- the GTL process consists of the three major sub-processes of (1) reforming of natural gas, (2) F-T synthesis of syngas and (3) reforming of product.
- the F-T reaction which is performed at a reaction temperature of 200 to 350 0 C and a pressure of 10 to 30 atm using iron and cobalt as catalyst can be described by the following four key reactions.
- the current reforming process of atmospheric residue or vacuum residue used in the refinery plant is a reliable one thanks to improvement of catalysts and processing techniques.
- the F-T synthetic oil further development of an adequate hydrocarbon reforming process is required, because there is a big difference in compositions and physical properties from the source material used in the refinery plant.
- the processes for treating the primary product of the F-T reaction include hydrocracking, dewaxing, isomerization, allylation, and so forth.
- the major products of the F-T reaction include naphtha/gasoline, middle distillates with a high centane number, sulfur- and aromatic-free liquid hydrocarbons, ⁇ -olefins, oxygenates, waxes, and so forth.
- iron- and cobalt-based catalysts are used for the F-T reaction.
- the iron- based catalysts were preferred in the past for F-T reaction.
- cobalt catalysts are predominant in order to increase the production of liquid fuel or wax and to improve conversion.
- Iron-based catalysts are characterized in that they are the most inexpensive F-T reaction catalysts producing less methane at high temperature and having high selectivity for olefins and the product can be utilized as source material in chemical industry as light olefin or ⁇ -olefin, as well as fuel.
- a lot of byproducts including alcohols, aldehydes, ketones, etc., are produced in addition to hydrocarbons.
- the iron-based catalyst mainly used in the low- temperature F-T reaction for wax production by Sasol comprises Cu and K components as cocatalyst and is produced by the precipitation using SiO 2 as binder.
- the Sasol's high-temperature F-T catalyst is prepared by melting magnetite, K, alumina, MgO, etc.
- Cobalt-based catalysts are more expensive than Fe catalysts. But, they have higher activity, longer lifetime and higher yield of liquid paraffin-based hydrocarbon production with less CO 2 generation. However, they can be used only at low temperature because the excessive CH 4 is produced at high temperature. Further, with the usage of expensive cobalt, the catalysts are prepared by dispersing on a stable support with a large surface area, such as alumina, silica, titania, etc. A small amount of a precious metal cocatalyst such as Pt, Ru, Re, etc., is added as cocatalyst.
- F-T synthesis reactors there are four types: circulating fluidized bed reactor, fluidized bed reactor, multitubular fixed bed reactor and slurry-phase reactor.
- the reactor should be adequately selected considering the syngas composition and the final product, because they have different reaction characteristics.
- the F-T process parameters are determined by the final product.
- the high-temperature F-T process for producing gasoline and olefin is carried out in the fluidized bed reactor and the low-temperature F-T process for producing wax and lubricant base oil is carried out in the multitubular fixed bed reactor (MTFBR) or in the slurry-phase reactor.
- MTFBR multitubular fixed bed reactor
- slurry-phase reactor Usually, linear-chain paraffins are produced by the F-T synthesis reaction, but C n H 2n compounds having double bonds, ⁇ -olefins or alcohols are obtained as the byproduct from side reactions.
- the surface properties of ⁇ - alumina may be transformed into, for example, that of boehmite because of the water produced during the reaction.
- the catalyst may become inactivated or thermal stability may be reduced due to the increased oxidation rate of the cobalt component support.
- there is a method of improving the stability of the catalyst by pretreating the surface of alumina using a silicon precursor [WO 2007/009680 Al].
- the aforesaid F-T catalysts show various specific surface areas, but the activity of the F-T reaction is known to be closely related with the particle size of the cobalt component, pore size distribution of the support and reducing tendency of the cobalt component. To improve these properties, a preparation method of the F-T catalyst by including the cobalt component through a well-known method on the support prepared through a complicated process is reported.
- the present inventors have demonstrated to develop a support comprising silica and alumina and having a bimodal pore structure in order to solve the aforementioned problems in an economical and efficient way.
- an alumina- silica support consisting of a predetermined proportion of Al 2 O 3 and SiO 2 having double-layered, bimodal pore structure of the larger and smaller pores in which alumina is dispersed on silica. This is formed as alumina with smaller pores is dispersed mainly on silica surface forming a double layer, thereby reducing the distribution of larger pores, provides much better heat- and matter-transfer performance than the conventional unimodal support with single-sized pores.
- silica surface is pre-treated by the alumina component, such chemical properties as dispersion of the activate component, electronic state, reducing property, etc., are improved, while comparing with two supports with different pore sizes are physically mixed, for a better production yield of liquid hydrocarbons attained through the F-T reaction.
- a catalyst prepared using the support particularly a catalyst including cobalt as active component, offers improved one-pass yield of carbon monoxide and hydrogen and long-term stability when used in the F-T reaction.
- the objective of the present invention is to provide an alumina-silica support comprising SiO 2 and Al 2 O 3 , having a predetermined specific surface area and having smaller and larger pores. This enables the catalyst to attain a high syngas conversion with minimized byproducts and a good long-term stability for a catalyst using the same and a preparation method of liquid hydrocarbons from a syngas using the same.
- the porous alumina-silica support of the present invention having a double-layered, bimodal pore structure, in which alumina is uniformly dispersed on silica surface.
- This leads to superior heat- and matter-transfer performance and, thus, an F-T reaction catalyst prepared using the same provides superior one-pass yield of the reactant carbon monoxide and the support is applicable to the preparation of catalysts for the competitive design and development of a GTL process with improved long-term stability and reduced cost for removing unreacted materials.
- Figure 1 shows carbon monoxide conversion and catalyst stability with time for the
- Figure 2 shows specific surface area and pore size distribution of the catalysts prepared in Examples 4 and 8 and Comparative Example 2.
- Figure 3(a) is the electron micrograph of the 20 wt% alumina-silica support prepared in Example 1 and Figure 3(b) is the electron micrograph of the 0.5 wt% Ru/20 wt% Co/20 wt% Zr/20 wt% alumina- silica catalyst prepared in Example 8.
- Figure 4(a) shows the surface EDS (energy-dispersive X-ray spectroscopy) analysis result of the 20 wt% alumina-silica support prepared in Example 1 and Figure 4(b) shows the surface EDS analysis result of the 0.5 wt% Ru/20 wt% Co/20 wt% Zr/20 wt% alumina- silica catalyst prepared in Example 8.
- the present invention is characterized by a double-layered alumina- silica support comprising 1 to 80 wt% of Al 2 O 3 and 20 to 99 wt% of SiO 2 , alumina particles being dispersed on silica surface, and having a bimodal pore structure with pores of a relatively smaller size PSi and pores of a larger size PS 2 ,
- the pore sizes PSi and PS 2 being in the range:
- the present invention is also characterized by a preparation method of an alumina- silica support having a bimodal pore structure with pores of a smaller size PSi and pores of a larger size PS 2 .
- the pore sizes PSi and PS 2 are being in the above range, comprising the steps of adding an aluminum alkoxide solution dissolved in an alcohol based solvent, silica gel slurry, organic carboxylic acid having a pK a value of 3.5 to 5 and water and heating at 80 to 130 0 C to prepare boehmite sol-silica gel; and baking the boehmite sol-silica gel at 200 to 700 0 C to prepare an alumina- silica support.
- a cobalt component or other active component is dispersed on a support having a large surface area, such as alumina, silica, titania, etc.
- a support having a large surface area such as alumina, silica, titania, etc.
- the dispersion and reducing property of the active component decreases, resulting in decrease of catalytic activity or accelerated inactivation of the catalyst.
- FTS Fischer- Tropsch synthesis
- the water produced during the reaction may cause the change of the surface property of the ⁇ -alumina to that of boehmite. Therefore, various methods of pretreatment with another component have been introduced to improve thermal stability of alumina.
- silica is used as a support, a stronger bonding between cobalt and the support than an alumina support is used results in the reduced reducing tendency to cobalt metal and consequently decreases the activity.
- a method is proposed to pretreat the silica surface with zirconium.
- the support of the present invention comprises the components Al 2 O 3 and SiO 2 , thereby solving the problems occurring when only one of the alumina and silica components are used.
- the bimodal pore structure attained by dispersing alumina on silica surface provides improved transfer of reaction heat and matters during the reaction as well as improving dispersion of cobalt in the process of including the active component cobalt in the support, thereby increasing FTS reaction activity.
- the support has a specific surface area ranging from 150 to 400 m 2/g and has a bimodal pore structure with pores of a smaller size PSi (2 nm ⁇ PSi ⁇ 4 nm) and pores of a larger size PS 2 (4 nm ⁇ PS 2 ⁇ 20 nm).
- the proportion of the specific surface area Si of the smaller pores to the specific surface area S 2 of the larger pores, or Si/S 2 , is maintained at 0.05 to 0.5. Since the distribution of the larger pores is relatively larger, the compounds having a high boiling point may be produced during the reaction are transferred efficiently, thereby inhibiting the inactivation of the catalyst.
- the support prepared in accordance with the present invention has a bimodal pore structure in which alumina is uniformly dispersed on silica pore surface. This is accomplished as only the smaller alumina pores are formed on silica pore surface as the alumina particles are uniformly dispersed as double layer, while the formation of relatively larger pores that may be formed between alumina particles is suppressed.
- the smaller pores are mainly due to the pores of alumina itself, while the larger pores are those of silica.
- the relatively larger distribution of larger pores than that of smaller pores provides superior heat- and matter-transfer performance and increased FTS reactivity due to the improved dispersion of cobalt or other active components.
- Various supports are known to consist of these properties.
- a catalyst prepared by baking with the metal oxides such as silica, alumina, etc. has a unimodal pore distribution with single-sized pores.
- the catalyst of the present invention has a bimodal pore structure with two different pore sizes.
- the pore size of the smaller pores is smaller than 2 nm, the production of byproducts such as carbon dioxide may increase because of insufficient heat- and matter- transfer performance. If the pores with a pore size larger than 100 nm exist in large amount, conversion may decrease due to the decrease of the specific surface area of the catalyst.
- the proportion of the specific surface area Si of the smaller pores of the pores size 2 to 4 nm and the specific surface area S 2 of the larger pores of the pores size 4 to 10 nm, or Si/S 2 is maintained at 0.05 to 0.5.
- the larger pores are mainly formed by silica and the smaller pores are formed by alumina. If the proportion of the specific surface area Si/S 2 is smaller than 0.05, the effect resulting from the bimodal pore structure decreases and, thus, FTS reactivity also decreases.
- the specific surface area Si/S 2 exceeds 0.5, the silica pores are clogged by alumina, which causes the decrease of the specific surface area of the alumina- silica support, which further decreases the dispersion of cobalt or other active components and, thereby, decreases the FTS reactivity.
- the modification of the alumina component during the reaction further decreases the FTS reactivity.
- the aforesaid range is preferred.
- the support of the present invention comprises 1 to 80 wt% of Al 2 O 3 and 20 to 99 wt% of SiO 2 . If the SiO 2 content exceeds 99 wt%, the silica support characteristics becomes dominant, and compounds of cobalt silicate are formed easily during the pre- treatment process because of strong interaction with the main active component cobalt, thereby reduces the F-T reactivity. If the content is below 20 wt%, the alumina support property becomes dominant, and causes the decrease of thermal stability and oxidation of the cobalt component may occur easily due to the deformation of the support by the water produced during the reaction.
- the specific surface area of the support of the present invention is maintained in the range from 150 to 400 m 2 /g.
- the specific surface area is smaller than 150 m 2 /g, the dispersion of cobalt decreases and, thus, FTS reactivity may also decreases. If it exceeds 400 m 2 /g, the formation of smaller pores with pore size PSi by alumina becomes dominant, so that the pores may be clogged during the process of including cobalt or other active components, resulting in the decrease of dispersion and, consequently, decrease of FTS reactivity. Hence, the aforesaid range is preferred.
- an aluminum alkoxide is dissolved in an alcohol based organic solvent to prepare an aluminum alkoxide solution.
- the alcohol based organic solvent one having 1 to 4 carbon atoms, having a boiling point no higher than 150 0 C and easy to dry is used.
- the alcohol based organic solvent may be selected from methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and 2-methylpropanol.
- the alcohol is used in 5 to 200 mols per 1 mol of the aluminum alkoxide. If it is used less than 5 mols, it is difficult to dissolve the aluminum alkoxide with the alcohol solvent. The content in excess of 200 mols is unfavorable for the reaction efficiency and also economically.
- boehmite sol-silica gel 0.01 to 1 mol of an organic carboxylic acid having a pK a value of 3.5 to 5 and 2 to 12 mols of water are added and heating is performed to prepare boehmite sol-silica gel. Then, hydrolysis occurs rapidly and a white, amorphous aluminum hydroxide precipitate is formed in the alcohol solvent, which is peptized by the organic acid to form nano-sized boehmite sol.
- the boehmite sol is an important factor affecting the crystal size and crystallinity, depending on the kind of an acid, amount of use and reaction temperature.
- a weak organic carboxylic acid having a pK a value of 3.5 to 5, for example, one selected from formic acid, acetic acid and propionic acid is used.
- the organic carboxylic acid is used in 0.01 to 1 mol, more preferably in the range 0.01 to 0.5 mol per 1 mol of the aluminum alkoxide. If less than 0.01 mol used the intended effect is not attained. If excess of the acid is used, the crystal size of boehmite decreases and the sol becomes transparent.
- the aluminum hydroxide formed by the hydrolysis of the aluminum alkoxide is peptized quickly, resulting in more crystalline nuclei of boehmite and, consequently forms smaller size crystals. Accordingly, the crystal size of boehmite can be easily controlled with the input amount of the acid. Thus the physical properties of boehmite like specific surface area, porosity, etc. can be controlled easily.
- the organic carboxylic acid may form bonding with aluminum to form aluminum tricarboxylate.
- the use of an organic acid is advantageous over the use of an inorganic acid, because it is easily removable at relatively low drying temperature and the resultant boehmite does not undergo changes in structure or crystal phase.
- the amount of the water used for the hydrolysis is maintained at minimum. It is used in 2 to 12 mols per 1 mol of the aluminum alkoxide. If it is used less than 2 mols, hydrolysis does not occur sufficiently. In excess of 12 mols used, the process of separation and recollection becomes complicated.
- the silica gel is obtained by mixing silica with a solvent.
- the solvent may be an organic solvent commonly used in the art. In the present invention, isopropyl alcohol is used.
- the solvent is used in 1 to 100 wt% per 1 wt% of silica. If it is used less than 1 wt%, it is difficult to effectively carry out the precipitation of alumina because of inadequate dispersion of the silica. The use of the solvent in excess of 100 wt% is unfavorable in reaction efficiency and economy.
- the reaction is performed at 80 to 130 0 C for 1 to 48 hours. If the reaction temperature is below 80 0 C, crystal growth of boehmite becomes slow, thereby resulting in the formation of impurities such as gibbsite and if it exceeds 130 0 C, the boehmite crystal may become too large.
- Such prepared boehmite sol-silica gel is baked at 200 to 700 0 C to prepare the alumina- silica support. If the baking temperature is below 200 0 C, the crystal growth of alumina is retarded and if it exceeds 700 0 C, specific surface area decreases abruptly due to the change of the alumina phase. Thus, the aforesaid range is preferable in preparing the alumina-silica support by synthesizing alumina in silica-dispersed slurry phase.
- the resultant support has a double layer structure with alumina dispersed on silica surface and a bimodal pore structure with both smaller and larger pores.
- the present invention is characterized by a catalyst prepared using the alumina- silica support. With pores of two different sizes, the support provides superior heat- and matter-transfer performance to the conventional support having single-sized pores and thus provides better catalytic activity.
- the present invention is particularly preferable for the catalyst used in the Fischer-
- the active component of the catalyst may be one commonly used in the art and is not particularly limited. Specifically, at least one of the transition metal selected from cobalt (Co), zirconia (Zr), ruthenium (Ru), rhenium (Re) and platinum (Pt) may be used.
- the metals are used in the form of precursors, such as nitrate salt, acetate salt, chloride salt, etc.
- cobalt (Co) is used as main component and zirconia (Zr) is supported or such precious metal component as ruthenium (Ru), rhenium (Re), platinum (Pt), etc. is added to improve dispersion and the reducing property of the main component cobalt (Co) prior to supporting cobalt.
- the improvement of the reducibility of the active component cobalt leads to long-term performance of the catalyst improved as oxidation by the water produced during the F-T reaction is prevented.
- the zirconia (Zr) used for the pre-treatment is 1 to 50 wt% per 100 wt% of the support.
- the content of zirconia is less than 1 wt%, the effect on the dispersion of the active component cobalt is slight. If it exceeds 50 wt%, the specific surface area of the support decreases abruptly and, thereby, the dispersion of the active component cobalt decreases.
- the additional component added in addition to the active component is used in 0.005 to 1 wt% per 100 wt% of the support. If the content is less than 0.005 wt%, the effect of the addition is not significant. If it exceeds 1 wt%, the catalyst man- ufacture cost increases and the selectivity for methane increases.
- the proportion of the support to the active component is in the range 60-95:5-40 wt%. If the content of the active component is less than 5 wt%, the yield of liquid hydrocarbons decreases because of insufficient F-T reactivity. If it exceeds 40 wt%, the catalyst manufacture cost is too high as compared with the improvement of F-T reactivity.
- the catalyst is prepared by the method commonly used in the art. Specifically, it is prepared by direct supporting, co-precipitation, etc., followed by baking.
- the baking is performed at 100 to 700 0 C, preferably at 150 to 600 0 C. If the baking temperature is below 100 0 C, the solvent and the precursor component may remain in the catalyst and cause the side reactions. If it exceeds 700 0 C, the particle size of the active component increases by sintering, which may result in the decrease of the dispersion of cobalt or other active component can lead to the decrease of the specific surface area of the support. Hence, it is preferable to maintain the aforesaid conditions.
- the present invention is also characterized by a preparation method of liquid hydrocarbons from a syngas by the Fischer- Tropsch reaction in the presence of the catalyst.
- the F-T reaction is performed using the catalyst in a fixed bed, a fluidized bed or a slurry reactor, in the temperature range of from 200 to 700 0 C, after reducing under hydrogen atmosphere.
- F-T reaction is performed under a standard condition, specifically at a temperature of 300 to 500 0 C, at a pressure of 30 to 60 kg/cm 2 and at a space velocity of 1000 to 10000 h ⁇ although not limited thereto.
- Such prepared catalyst provides an F-T reaction conversion of 25 to 99 mol% and a selectivity for hydrocarbons with five carbon atoms or more, specifically naphtha, diesel, middle distillate, heavy oil, wax, etc., of 25 to 86 mol%.
- a silica gel slurry was prepared by mixing 20 g of silica having a specific surface area of 300 m 2 /g and a pore size of 15 nm with 100 g of isopropyl alcohol (2-propanol). After mixing aluminum isopropoxide with the silica gel slurry, acetic acid and water were slowly added. Amorphous aluminum hydroxide was obtained by hydrolysis.
- the molar proportion of the reactants aluminum isopropoxide, 2-propanol, acetic acid and water was maintained at 1 : 25 : 0.035 : 3 and the content of the aluminum isopropoxide (based on alumina) was maintained at 20 wt% per 100 wt% of the silica gel slurry (based on silica).
- the silica gel slurry and the amorphous aluminum hydroxide were heated for 20 hours at 85 0 C under reflux to prepare boehmite sol-silica gel, which was baked at 500 0 C for over 5 hours to prepare a 20 wt% alumina- silica support.
- the prepared catalyst had a specific surface area of 228 m 2 /g and a bimodal pore structure having smaller pores with a pore size of 2 to 4 nm and larger pores with a pore size of 4 to 10 nm, the proportion of the specific surface area Si of the smaller pores to the specific surface area S 2 of the smaller pores, or Si/S 2 , being 0.111.
- An alumina support was prepared in the same manner as in Example 1, except for excluding the silica gel slurry.
- the prepared alumina support had a specific surface area of 455 m 2 /g.
- alumina- silica support was prepared in the same manner as in Example 1, except for supporting zirconium before supporting cobalt on the alumina-silica support as active component.
- About 0.981 g of a zirconium precursor (ZrCl 2 O8H 2 O) was dissolved in 60 mL of deionized water and supported on 5 g of the 20 wt% alumina- silica support.
- the prepared catalyst had a specific surface area of 214 m 2 /g and a bimodal pore structure of smaller pores with a pore size of 2 to 4 nm and larger pores with a pore size of 4 to 10 nm, the proportion of the specific surface area Si of the smaller pores to the specific surface area S 2 of the smaller pores, or Si/S 2 , being 0.122.
- Fischer- Tropsch reaction was performed using the prepared catalyst.
- a 20 wt% Co/20 wt% Zr/20 wt% Al 2 O 3 -SiO 2 catalyst was prepared in the same manner as in Example 2, except for using 3.925 g (20 wt% per the support based on metal weight) of a zirconium precursor (ZrCl 2 O8H 2 O). Fischer- Tropsch reaction was performed using the prepared catalyst.
- An alumina- silica support was prepared in the same manner as in Example 2, except for, after supporting the cobalt component, drying in an oven of 100 0 C for over 12 hours. Subsequently, a 0.5 wt% Ru/20 wt% Co/5 wt% Zr/20 wt% Al 2 O 3 -SiO 2 catalyst was prepared by supporting 0.065 g (0.5 wt% per the support based on metal weight) of a ruthenium precursor (RuCl 3 3H 2 O) and then baking at 400 0 C for 5 hours under air atmosphere.
- a ruthenium precursor RuCl 3 3H 2 O
- the prepared catalyst had a specific surface area of 204 m 2 /g and a bimodal pore structure of smaller pores with a pore size of 2 to 4 nm and larger pores with a pore size of 4 to 10 nm, the proportion of the specific surface area Si of the smaller pores to the specific surface area S 2 of the smaller pores, or Si/S 2 , being 0.135.
- Fischer- Tropsch reaction was performed using the prepared catalyst.
- Example 5 An alumina- silica support was prepared in the same manner as in Example 2, except for, after supporting the cobalt component, drying in an oven of 100 0 C for over 12 hours. Subsequently, a 0.5 wt% Ru/20 wt% Co/5 wt% Zr/20 wt% Al 2 O 3 -SiO 2 catalyst was prepared by supporting 0.078 g (0.5 wt% per the support based on metal weight) of a ruthenium precursor (Ru(NO)(NO 3 ) 3 ) and then baking at 400 0 C for 5 hours under air atmosphere.
- a ruthenium precursor Ru(NO)(NO 3 ) 3
- the prepared catalyst had a specific surface area of 204 m 2 /g and a bimodal pore structure of smaller pores with a pore size of 2 to 4 nm and larger pores with a pore size of 4 to 10 nm, the proportion of the specific surface area Si of the smaller pores to the specific surface area S 2 of the smaller pores, or Si/S 2 , being 0.135.
- Fischer- Tropsch reaction was performed using the prepared catalyst.
- a catalyst consisting 0.5 wt% Ru/20 wt% Co/10 wt% Zr/20 wt% A12O3-SiO2 was prepared in the same manner as in Example 4, except for using 1.963 g (10 wt% per the support based on metal weight) of a zirconium precursor (ZrCl 2 O8H 2 O). Fischer- Tropsch reaction was performed using the prepared catalyst.
- a catalyst consisting 0.5 wt% Ru/20 wt% Co/15 wt% Zr/20 wt% A12O3-SiO2 catalyst was prepared in the same manner as in Example 4, except for using 2.944 g (15 wt% per the support based on metal weight) of a zirconium precursor (ZrCl 2 O8H 2 O). Fischer- Tropsch reaction was performed using the prepared catalyst.
- a catalyst consisting 0.5 wt% Ru/20 wt% Co/20 wt% Zr/20 wt% Al 2 O 3 -SiO 2 catalyst was prepared in the same manner as in Example 4, except for using 3.925 g (20 wt% per the support based on metal weight) of a zirconium precursor (ZrCl 2 O8H 2 O).
- the prepared catalyst had a specific surface area of 172 m 2 /g and a bimodal pore structure of smaller pores with a pore size of 2 to 4 nm and larger pores with a pore size of 4 to 10 nm, the proportion of the specific surface area Si of the smaller pores to the specific surface area S 2 of the smaller pores, or Si/S 2 , being 0.414.
- Fischer- Tropsch reaction was performed using the prepared catalyst.
- a catalyst consisting 0.5 wt% Ru/20 wt% Co/5 wt% Zr/10 wt% Al 2 O 3 -SiO 2 catalyst was prepared in the same manner as in Example 4, except for maintaining the content of the aluminum isopropoxide (based on alumina) at 10 wt% per 100 wt% of the silica gel slurry (based on silica). Fischer-Tropsch reaction was performed using the prepared catalyst.
- a catalyst consisting 0.5 wt% Ru/20 wt% Co/5 wt% Zr/30 wt% Al 2 O 3 -SiO 2 catalyst was prepared in the same manner as in Example 4, except for maintaining the content of the aluminum isopropoxide (based on alumina) at 30 wt% per 100 wt% of the silica gel slurry (based on silica).
- the prepared catalyst had a specific surface area of 218 m 2 / g and a bimodal pore structure of smaller pores with a pore size of 2 to 4 nm and larger pores with a pore size of 4 to 10 nm, the proportion of the specific surface area Si of the smaller pores to the specific surface area S 2 of the smaller pores, or Si/S 2 , being 0.212.
- Fischer-Tropsch reaction was performed using the prepared catalyst.
- An alumina- silica support was prepared in the same manner as in Example 8, except for, after supporting 3.819 g (15 wt% based on metal weight) of the cobalt nitrate salt precursor (Co(NO 3 ) 2 6H 2 O), drying in an oven of 100 0 C for over 12 hours. Subsequently, a 0.5 wt% Ru/ 15 wt% Co/20 wt% Zr/20 wt% Al 2 O 3 -SiO 2 catalyst was prepared by supporting a 0.5 wt% of a ruthenium precursor (RuCl 3 3H 2 O) per 100 wt% of the support and baking.
- RuCl 3 3H 2 O ruthenium precursor
- the prepared catalyst was reduced with hydrogen at 400 0 C for 12 hours and introduced to a slurry reactor after sealing. 300 mL of squalane was added as solvent in the slurry reactor. After adding 5 g of the catalyst, another reduction was performed at 220 0 C for over 12 hours.
- a catalyst was prepared and Fischer- Tropsch was performed in the same manner as in Example 9, except for increasing the temperature to 240 0 C.
- the contents of the product of the Fischer- Tropsch reaction are summarized in Table 1. The steady-state condition was obtained after around 30 h operation and the averaged values for 10 hours at the steady-state were taken.
- Example 1 except for maintaining the molar proportion of the reactants aluminum iso- propoxide, 2-propanol, acetic acid and water was maintained at 1 : 25 : 0.5 : 6 and maintaining the content of the aluminum isopropoxide (based on alumina) at 20 wt% per 100 wt% of the silica gel slurry (based on silica).
- the prepared alumina support had a specific surface area of 350 m 2 /g.
- a 20 wt% Co/20 wt% Al 2 O 3 -SiO 2 catalyst was prepared using the 20 wt% alumina- silica support.
- the prepared catalyst had a specific surface area of 194 m 2 /g and a bimodal pore structure of smaller pores with a pore size of 2 to 4 nm and larger pores with a pore size of 4 to 10 nm.
- the proportion of the specific surface area Si of the smaller pores to the specific surface area S 2 of the smaller pores, or Si/S 2 is 0.905.
- Fischer- Tropsch reaction was performed using the prepared catalyst.
- a 0.5 wt% Ru/20 wt% Co/5 wt% Zr/SiO 2 catalyst was prepared in the same manner as in Example 4, except for using silica gel alone as a support, i.e., excluding alumina. Fischer- Tropsch reaction was performed using the prepared catalyst.
- a 20 wt% Co/ Al 2 O 3 catalyst was prepared in the same manner as in Example 1, except for using alumina having a specific surface area or 455 m 2 /g alone as a support. Fischer- Tropsch reaction was performed using the prepared catalyst.
- a 0.5 wt% Ru/20 wt% Co/5 wt% Zr/ Al 2 O 3 catalyst was prepared in the same manner as in Example 4, except for using alumina having a specific surface area or 455 m 2 /g alone as a support. Fischer-Tropsch reaction was performed using the prepared catalyst.
- An alumina- silica support was prepared in the same manner as in Example 4, by the previously known alumina synthesis method. 10 g of silica gel having a specific surface area of 300 m 2 /g and a pore size of 15 nm was mixed with 400 mL of deionized water to prepare the slurry of silica gel. A boehmite-silica gel support was prepared in a three-neck flask reactor maintained at 70 0 C by co-precipitation, using 15.02 g of aluminum silicate (A1(NO 3 ) 3 9H 2 O) as alumina precursor and 14.94 g of sodium carbonate (Na 2 CO 3 ) as precipitant.
- a boehmite-silica gel support was prepared in a three-neck flask reactor maintained at 70 0 C by co-precipitation, using 15.02 g of aluminum silicate (A1(NO 3 ) 3 9H 2 O) as alumina precursor and 14.94 g of sodium carbonate (Na 2
- the content of aluminum silicate (based on alumina) was maintained at 20 wt% per 100 wt% of the silica gel slurry (based on silica).
- the cake obtained after filtering and washing was baked at 500 0 C for over 5 hours to prepare an alumina-silica support.
- a 0.5 wt% Ru/20 wt% Co/5 wt% Zr/20 wt% A12O3-SiO2 catalyst was prepared in the same manner as in Example 4.
- the prepared catalyst had a specific surface area of 135 m 2 /g. Fischer-Tropsch reaction was performed using the prepared catalyst.
- the alumina-silica supports prepared in accordance with the present invention had a bimodal pore structure with larger and smaller pores.
- the catalytic stability and one-pass yield of carbon monoxide improved as compared with the conventional F-T reaction catalysts (Comparative Examples 1 to 4).
- Comparative Example 4 Although the same alumina- silica support was used in Comparative Example 4 as that of the present invention, specific surface area was smaller and a bimodal pore structure was not attained due to the difference in preparation method. As a result, CO conversion was smaller and reaction efficiency decreased significantly due to the accelerated inactivation of the catalyst as the pores were clogged by the compounds having a high boiling point produced during the reaction.
- zirconium which is known to improve the dispersion of the major active component cobalt and provide a reduction state of cobalt metal suitable for the F-T reaction, showed difference in catalytic activity and stability depending on the content (Examples 6, 7 and 8).
- the stability of the F-T catalyst improved when the zirconium content was at least 20 wt%.
- Figure 1 shows carbon monoxide conversion and catalyst stability with time passage for the Fischer-Tropsch reaction performed using the catalysts prepared in Examples 1, 4, 7 and 8 and Comparative Examples 1 to 4.
- Figure 2 shows specific surface area and pore distribution of the catalysts prepared in Examples 4 and 8 and Comparative Example 2. The superiority of the Examples over the Comparative Examples can be ascertained.
- Figure 3(a) is the electron micrograph of the 20 wt% alumina-silica support prepared in Example 1 and Figure 3(b) is the electron micrograph of the 0.5 wt% Ru/20 wt% Co/20 wt% Zr/20 wt% alumina- silica catalyst prepared in Example 8.
- alumina is uniformly dispersed on silica surface in the form of spherical nanoparticles.
- Figure 3(b) shows nano-sized particles are more uniformly dispersed on silica surface through several pre-treatment processes.
- Figure 4 shows the surface elementary components of the catalysts provided by the present invention.
- Figure 4(a) shows the surface EDS analysis result of the 20 wt% alumina- silica support prepared in Example 1.
- Zr was a Pt coating material for SEM analysis.
- Al content was 13% and Si content was 87%.
- Figure 4(b) shows the surface EDS analysis result of the 0.5 wt% Ru/20 wt% Co/20 wt% Zr/ 20 wt% alumina-silica catalyst prepared in Example 8.
- Zr was a Pt coating material for SEM analysis, too.
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