CN101868299B - 具有改进的活性维持性的钴催化剂 - Google Patents
具有改进的活性维持性的钴催化剂 Download PDFInfo
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- CN101868299B CN101868299B CN200880113432.6A CN200880113432A CN101868299B CN 101868299 B CN101868299 B CN 101868299B CN 200880113432 A CN200880113432 A CN 200880113432A CN 101868299 B CN101868299 B CN 101868299B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 239000010941 cobalt Substances 0.000 title claims abstract description 36
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 33
- 230000000694 effects Effects 0.000 title description 8
- 238000012423 maintenance Methods 0.000 title description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 9
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 33
- 238000001354 calcination Methods 0.000 claims description 23
- IAGCDJZAYOZMCS-UHFFFAOYSA-N 2-hydroxypropanoic acid;titanium Chemical compound [Ti].CC(O)C(O)=O IAGCDJZAYOZMCS-UHFFFAOYSA-N 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 11
- 150000001869 cobalt compounds Chemical class 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000012018 catalyst precursor Substances 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052622 kaolinite Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 claims 1
- 150000001868 cobalt Chemical class 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 claims 1
- 150000003893 lactate salts Chemical class 0.000 claims 1
- 238000005259 measurement Methods 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000010936 titanium Substances 0.000 abstract description 11
- 229910052719 titanium Inorganic materials 0.000 abstract description 11
- 239000013522 chelant Substances 0.000 abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 238000007598 dipping method Methods 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 239000003426 co-catalyst Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- LFSBSHDDAGNCTM-UHFFFAOYSA-N cobalt(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Co+2] LFSBSHDDAGNCTM-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
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- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
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- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
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- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 isopropyl alcohols Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/005—Spinels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- B01J35/30—
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
本发明提供了一种包含催化金属(优选钴、铼或其混合物)的催化剂。该催化金属负载在源自锐钛矿型二氧化钛的包含多数量的二氧化钛和少数量的铝酸钴的载体上。该载体还包含少数量的源自钛螯合物的二氧化钛。
Description
发明领域
本发明涉及一种包含负载在二氧化钛和铝酸钴载体上的钴的催化剂。其还涉及一种用于改进该催化剂的活性维持性的方法,以及其在烃合成中的用途。
发明背景
已知包含负载在载体如二氧化硅或氧化铝上的钴的催化剂能用于加氢反应,例如醛和腈的加氢。它们也用于通过费-托工艺(Fischer-Tropsch process)合成烃。
助催化剂金属(例如铼、锆、锰等)通常与钴一同使用,以改进催化性能的各个方面。
在费-托合成工艺的情况下,尤其是在淤浆鼓泡塔反应器(slurry bubblecolumn reactor)中进行时,优选的催化剂包括负载在二氧化钛载体上的钴。一般来说,这种催化剂中的二氧化钛是其金红石型。
在美国专利公开2004/0204506 A1(在此将其全文结合到本文中)中公开了一种改进的催化剂载体,其主要包含由其锐钛矿型转化为其金红石型的二氧化钛,以及少数量的包含铝酸钴的粘结剂。通过用氧化铝粘结剂形成二氧化钛载体并随后使该氧化铝粘结剂与其量足以将至少部分(优选基本全部)该氧化铝转化为铝酸钴的钴化合物反应,将铝酸钴加入到金红石型二氧化钛载体中。通常还形成了少量的钛酸钴。为方便起见,本文中将这种载体称为“钛酸盐载体”。已经证实包括在该“钛酸盐载体”上的钴、铼或其混合物的催化剂改进了在费托工艺中制备高级烃的选择性。
发明概述
目前已经发现通过将少数量的源自钴螯合物的TiO2加入到催化剂中改进了包含在“钛酸盐载体”上的钴的催化剂的活性维持性。可以在将催化金属负载在“钛酸盐载体”上之前或在将催化金属负载在“钛酸盐载体”的过程中,将源自钛螯合物的TiO2加入到催化剂中。
因此,在本发明的一个实施方案中,提供了一种催化剂,其包含:催化金属,优选为钴、铼或其混合物;源自锐钛矿二氧化钛的包含多数量的二氧化钛和少数量的铝酸钴的催化剂载体;以及少数量的源自钛螯合物的二氧化钛。
在本发明的一个实施方案中,提供了一种负载在包含多数量的二氧化钛少数量的铝酸钴的载体上的含钴催化剂前体的制备方法,其包括以下中的一种:
(a)用钛螯合物处理载体,在高于约250℃的温度下煅烧经过如此处理的载体从而由钛螯合物生成TiO2,然后用经过煅烧的载体负载钴化合物;或
(b)同时用钛螯合物和钴化合物处理载体,然后在高于约250℃的温度下煅烧经过如此处理的载体。
从下面的详述中,本发明的这些和其它实施方案将变得显而易见。
发明详述
用于本发明催化剂的载体包括多数量的二氧化钛和少数量的铝酸钴粘结剂。非必要地,该载体还可包含氧化硅或氧化铝粘结剂,但优选该载体基本不含氧化铝。通常,该载体将包含至少50wt%二氧化钛,优选80wt%-90wt%二氧化钛。优选60-98wt%的二氧化钛为金红石晶体相。粘结剂中铝酸钴的量取决于在载体形成中所用的钴和铝化合物的量。提供大于0.25(优选0.5-2,更优选约1)的钴/铝原子比就可以说足够的钴存在于该载体中。因此,在Co/Al比为0.25时,约一半的氧化铝作为铝酸钴存在。在Co/Al比为0.5时,基本所有存在的氧化铝都以铝酸钴存在。在Co/Al比大于0.5时,除铝酸钴之外,该载体还将包含钛酸钴而基本上不合氧化铝。优选该载体将包含钛酸钴,例如,占载体总重量的约4-12wt%。
如前所述,该粘结剂还可以包含氧化铝和非必要的二氧化硅。通常,该粘结剂小于载体的约30wt%,优选小于载体的约15wt%。典型地,该粘结剂大于该载体的约3wt%。二氧化硅的量小于粘结剂总量的50wt%,优选为粘结剂的35wt%。
典型地,载体将具有约5m2/g-约40m2/g、优选10m2/g-30m2/g的表面积。孔体积在约0.2cc/g-约0.5cc/g、优选0.3cc/g-0.4cc/g的范围内。
典型地,通过将二氧化钛、氧化铝粘结剂材料与非必要的二氧化硅粘结剂材料的适当水性浆料喷雾干燥到一个出口温度为约105℃-135℃的热空气吹扫的腔室内而形成载体。喷雾干燥生成尺寸范围为约20-120微米的球形载体。然后将该经过喷雾干燥的载体在400℃-800℃范围内(优选约700℃)的温度下煅烧。然后,用钴化合物(优选硝酸钴)的水溶液,以足以使得一经煅烧至少部分氧化铝转化为铝酸钴的量浸渍该经过煅烧的材料。优选使用足够的钴化合物以将50%至99+%的氧户铝转化为铝酸钴。因而,在载体的制备过程中添加的钴化合物的量将对应于在0.25∶1-2∶1(优选0.5∶1-1∶1)范围内的Co∶Al原子比。事实上,特别优选所制备的载体基本不含氧化铝。
典型地,在约700℃-约1000℃范围内(优选在约800℃-约900℃范围内)的温度下在空气中煅烧钴浸渍的载体。
在本发明的一个实施方案中,用足以使得钛螯合物一经煅烧将少数量的TiO2与载体结合的量的水溶性钛螯合物处理咳载体。可以使用的钛螫合物包括一种或多种具有2-约10个碳原子的线型或支化有机羧酸的那些。优选的螯合物是乳酸钛。
乳酸钛是一种水溶性盐,其可以制成以下两种形式:一种具有单个乳酸盐配体,另一种具有两个乳酸盐配体。任何一种形式都可以应用于本发明中。
方便地,通过用乳酸钛的水溶液浸渍载体并然后在高于约250℃(优选在约250-约500℃范围内)的温度下在空气中将经过浸渍的载体煅烧足以将乳酸钛转化为TiO2的时间,用乳酸钛处理该“钛酸盐载体”。通常,煅烧将进行约30分钟-约24小时。
源自乳酸钛的TiO2在载体上的负载量似乎并不至关重要。添加的TiO2量为0.3-1.0wt%的催化剂对活性维持性具有相同的有益作用。优选在将乳酸钛煅烧之后TiO2的量为约0.5wt%。
当由该载体制备费-托催化剂前体时,将对费-托合成具有催化活性的金属与载体复合。优选的金属为来自元素周期表第VIII族的那些,特别是铁、钴和钌,优选钴和钌,最优选钴。还可以采用助催化剂,如锆、钛、铼、铪、铈、钍和铀,以及本领域技术人员公知的其它助催化剂。该一种或多种金属以对于费-托合成具有催化活性的量存在,并且该量将随所选择的金属而变化。例如,在这种环境中钌比钴更具活性,因而钌以在约0.5-3.0wt%范围内的量使用,而钴将优选以约2-40wt%(更优选5-30wt%、进一步更优选10-25wt%)的量使用。
当采用助催化剂时,它们以少于活性催化金属的量使用,例如基于活性金属,以约1/20-1/10的重量比。最优选的催化剂是包含钴和铼、钴和钌以及钴和氧化钍的那些,特别是钴和铼。
可以用本领域技术人员公知的各种技术制备催化剂,包括浸渍(或者与助催化剂共浸渍或连续浸渍-通过喷雾干燥或通过初期润湿技术)。由于用于固定床费-托工艺的优选催化剂为其中该催化金属存在于催化剂颗粒的较外部分中(即在深度不超过250微米、优选深度不超过200微米的层中)的催化剂,因此制备该催化剂的优选方法为美国专利号5,140,050(通过参考引入本文域EP 0,266,898(通过参考引入本文)中描述的喷雾方法。对于淤浆费-托工艺,催化剂优选通过经过喷雾干燥的载体的初期润湿浸渍来制备。当采用该初期润湿浸渍技术时,非必要地采用有机浸渍助剂。这类助剂描述在美国专利No.5,856,260、美国专利No.5,856,261和美国专利No.5,863,856中,所有都通过参考引入本文。
因此,该载体可以用一种或多种催化金属化合物的溶液进行处理,然后煅烧。典型地,煅烧将在高于约250℃(优选在约250℃-约500℃的范围内)的温度下在空气中进行。
在包含钴和铼的费-托催化剂的优选情况中,用Re∶Co重量比在约0.005∶1-约0.2∶1范围内的硝酸钴和高铼酸的溶液处理载体。
在本发明另一可替代的且优选的实施方案中,用还包含乳酸钛的一种或多种催化金属化合物的溶液处理“钛酸盐载体”,然后在高于约250℃的温度下在空气中煅烧经过如此处理的载体。
通过使前体与还原剂(通常为氢气)在约250℃-约550℃(优选约275℃-约420℃)的范围内的温度下在环境压力-约40atm的压力下接触约0.5小时-约24小时,以活化该催化剂前体提供催化剂。
依照本发明制备的催化剂特别适用于通过费-托合成工艺合成烃。
费-托合成是公知的工艺,反应条件已经描述在可以获得的文献中。例如,温度可以在约175℃-约400℃、优选约180℃-250℃的范围内,而压力可以在约1-100巴、优选约15-40巴的范围内。氢/CO比可以在0.5/1-约4/1、优选约1.7/1-2.5/1的范围内,最优选为其化学计量量加或减约3%。由本发明的载体制得的催化剂优选用在淤浆(例如淤浆鼓泡塔反应器)中,其中气时空速可以在约1,000-25,000范围内。一种优选的淤浆鼓泡塔操作描述在美国专利No.5,348,982中,通过参考引入本文。由本发明的方法制备的产品大体上遵循舒尔茨-弗洛里(Schulz-Flory)分布,不同的是甲烷产率通常高于此分布所预测。这表明甲烷显然是由另外的机理生成的。
通常通过使全部或部分C5+烃进行分级和/或转化,将在上述工艺中生成的烃升级为更具价值的产物。“转化”是指其中至少一部分烃的分子结构被改变的一种或多种操作,其包括非催化处理(例如蒸汽裂化)和催化处理(例如其中将该部分或级分与适宜的催化剂接触的催化裂化)。如果氢作为反应物存在,则这类工艺步骤通常称作加氢转化,并且分别称作加氢异构化、加氢裂化、加氢脱蜡、加氢精制等。更严格的加氢精制通常称作加氢处理。这些反应是在文献中针对烃原料(包括富含链烷烃的烃原料)的加氢转化详细披露的条件下进行的。通过这些工艺由这类原料制备的更具价值的产物的示例性而非限定性的实例包括合成原油、液体燃料、乳液、纯化烯烃、溶剂、单体或聚合物、润滑油、药用油、含蜡烃、各种含氮或含氧产物等。液体燃料的实例包括汽油、柴油燃料和喷气式发动机燃料,而润滑油包括汽车用油、喷气机油和汽轮油等。工业用油包括钴井流体、农用油、传热油等。
认识到在不脱离如上所述的本发明的范围和精神的情况下,本发明的实施中的各种其它实施方案和改变对于本领域普通技术人员将是显而易见的且易于做出的。因此,不期望所附权利要求的范围被限于以上列出的确切描述,而是希望将权利要求解释为包含存在于本发明中的所有具有专利性的新颖特征,包括由本发明所属领域技术人员可作为其等同物处理的所有特征和实施方案。在以下实施例中进一步描述了本发明。
实施例
A.制备单乳酸钛
将293克部分的异丙醇钛加入110克乳酸和200克异丙醇的搅拌溶液中,然后加入350克去离子水。将该混合物缓慢加热以蒸馏掉异丙醇,得到的最终重量为480克。将该混合物过滤通过0.2微米的antek过滤器以除去非常少量的固体。用620克去离子水稀释348克部分的滤液以制得乳酸钛储备溶液。通过向少部分中加入氢氧化钠并通过过滤回收沉淀物来测量溶液中的钛浓度。将沉淀物干燥,在700℃煅烧,并称重。该分析的结果显示该乳酸钛储备溶液包含8.15wt%当量的TiO2。
B.催化剂的制备
用依据US 6,117,814通过喷雾干燥Degussa P-25TiO2与6wt%的由9∶1重量比的氧化铝与二氧化硅构成的粘结剂制备的载体开始制备一系列催化剂。对于表1中所列的催化剂A-D,通过下述方法将载体转化为“钛酸盐载体”:(a)在700℃煅烧经过喷雾干燥的载体,(b)使用硝酸钴的水溶使用约6wt%Co浸渍该载体;(c)在400℃煅烧该经过浸渍的载体和(d)在871℃再次煅烧,以将基本所有的氧化铝粘结剂转化为铝酸钴。对于催化剂E和F,不用钴处理载体,仅在1000℃煅烧。
对于除了使用高铼酸铵的催化剂E之外的所有催化剂,通过硝酸钴(15wt%Co)和高铼酸(Re∶Co重量比为0.09∶1.0)的水溶液的初期润湿浸渍制备催化剂。在浸渍之后,将催化剂在250℃煅烧。对于催化剂A、B和F,浸渍溶液中还包含乳酸钛储备溶液。用于催化剂A的浸渍溶液中还包含丙二酸,其中丙二酸:钴的摩尔比为0.3∶1.0。
应用两次浸渍和煅烧以得到表1中列出的最终负载量。
表1
C.活性维持性测定
在固定床单元中对表1中的催化剂进行长期的运行测试,以测定活性维持性。用氢将约1.3cc的用石英稀释的催化剂的装料在375℃、280psig下还原1小时。在低温下启动后,设定条件以在215℃、280psig和约7200cc标准条件气体/cc催化剂/小时的GHSV下由包含约64%H2、31%CO、3%Ar和2%N2的原料产生约60-70%的CO转化率。通过用N2作为内部标准的GC测定CO转化率。活性速率常数K是基于CO转化率、气体组成、温度、压力以及GHSV使用经验的专用动力学模型计算的。一级失活速率(由delta lnK/天计算的半衰期)是基于从第10天直到运行结束得到的速率数据。结果总结在表2中。从半衰期数据清楚地看出本发明的催化剂A和B比其他催化剂明显更稳定。这种优点通过向该载体的“钛酸盐”形式中添加少量源自乳酸钛的TiO2而获得。实施例F相比于E,显示将乳酸钛添加到基础型金红石TiO2-Al2O3-SiO2载体中并没有任何改进。
表2
Claims (12)
1.一种催化剂载体组合物,其包含:
a)多数量的二氧化钛;
b)少数量的包含铝酸钴的粘结剂,其中钴和氧化铝的原子比大于0.25;以及
c)少数量的独立于组分a)的TiO2,其源自基于载体总重量0.3wt%-1wt%的专门添加的乳酸钛,
其中根据增加的半衰期测量,该催化剂载体组合物与没有组分b)和c)中之一或没有这两者的对比催化剂载体组合物相比具有增加的稳定性。
2.权利要求1的组合物,其中钴和氧化铝的原子比大于0.5。
3.权利要求1的组合物,其中粘结剂占载体的3wt%-15wt%。
4.权利要求3的组合物,其中粘结剂包含0wt%-35wt%的二氧化硅。
5.一种制备催化剂载体的方法,其包括:
将主要包含二氧化钛且包含少数量的氧化铝以及非必要地包含少数量的二氧化硅的材料喷雾干燥,以形成喷雾干燥的产物;
将钴化合物加入到该喷雾干燥的产物中以提供含钴材料,钴化合物的加入量足以使得一经煅烧该氧化铝的至少一部分转化为铝酸钴;
在700℃-1000℃在空气中煅烧该含钴材料;
用添加的乳酸钛处理经过煅烧的钴材料,该乳酸钛的用量足以通过将该经过如此处理的材料煅烧而提供少数量的TiO2;
在高于250℃下在空气中煅烧该经过处理的材料以将乳酸盐转化为TiO2,从而形成权利要求1所述的催化剂载体组合物。
6.权利要求5的方法,其中钴的加入量足以提供0.25∶1-2∶1的Co/Al原子比。
7.权利要求5的方法,其中乳酸钛的量足以经煅烧提供基于该载体总重量0.3wt%-1wt%的TiO2。
8.一种催化剂,其包含:
催化活性金属或催化活性金属的混合物,以及权利要求1-4任一项所述的载体,其中金属选自基本上由钴、铼及其混合物构成的组。
9.一种负载在包含多数量的二氧化钛和少数量的铝酸钴的载体上的含钴催化剂前体的制备方法,其包括以下中的一种:
(a)用乳酸钛处理该载体,在高于250℃的温度下煅烧经过如此处理的载体从而由该乳酸钛生成TiO2,然后在经过煅烧的载体上负载钴化合物;和
(b)同时用乳酸钛和钴化合物处理该载体,然后在高于250℃的温度下煅烧经过如此处理的载体,从而形成权利要求8所述的催化剂。
10.权利要求9的方法,其中乳酸钛的用量足以经煅烧该乳酸盐提供0.3wt%-1wt%的TiO2。
11.权利要求9的方法,且包括步骤(a)。
12.权利要求9的方法,且包括步骤(b)。
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2008
- 2008-10-10 US US12/287,543 patent/US8722570B2/en active Active
- 2008-10-24 WO PCT/US2008/012088 patent/WO2009055013A2/en active Application Filing
- 2008-10-24 CN CN200880113432.6A patent/CN101868299B/zh not_active Expired - Fee Related
- 2008-10-24 JP JP2010531042A patent/JP5688291B2/ja not_active Expired - Fee Related
- 2008-10-24 EP EP08842206A patent/EP2217369A2/en not_active Withdrawn
- 2008-10-24 CA CA2702757A patent/CA2702757A1/en not_active Abandoned
- 2008-10-24 AU AU2008317382A patent/AU2008317382B2/en not_active Ceased
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0370757A1 (en) * | 1988-11-23 | 1990-05-30 | Exxon Research And Engineering Company | Titania-containing catalysts, their preparation and use in Fischer-Tropsch synthesis |
US6124367A (en) * | 1998-02-10 | 2000-09-26 | Exxon Research And Engineering Company | Titania catalysts, their preparation and use in fischer-tropsch synthesis |
CN1774407A (zh) * | 2003-04-11 | 2006-05-17 | 埃克森美孚研究工程公司 | 二氧化钛与铝酸钴催化剂载体的制备及其在费-托合成中的用途 |
Also Published As
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JP2011502038A (ja) | 2011-01-20 |
WO2009055013A3 (en) | 2009-06-25 |
AU2008317382B2 (en) | 2013-06-27 |
EP2217369A2 (en) | 2010-08-18 |
CA2702757A1 (en) | 2009-04-30 |
JP5688291B2 (ja) | 2015-03-25 |
US8722570B2 (en) | 2014-05-13 |
AU2008317382A1 (en) | 2009-04-30 |
WO2009055013A2 (en) | 2009-04-30 |
CN101868299A (zh) | 2010-10-20 |
US20090111899A1 (en) | 2009-04-30 |
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