CA2468328A1 - Catalyst containing microporous zeolite in mesoporous support and method for making same - Google Patents
Catalyst containing microporous zeolite in mesoporous support and method for making same Download PDFInfo
- Publication number
- CA2468328A1 CA2468328A1 CA002468328A CA2468328A CA2468328A1 CA 2468328 A1 CA2468328 A1 CA 2468328A1 CA 002468328 A CA002468328 A CA 002468328A CA 2468328 A CA2468328 A CA 2468328A CA 2468328 A1 CA2468328 A1 CA 2468328A1
- Authority
- CA
- Canada
- Prior art keywords
- zeolite
- inorganic oxide
- mixture
- temperature
- mesopores
- 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.)
- Abandoned
Links
- 239000010457 zeolite Substances 0.000 title claims abstract description 86
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 84
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 title claims description 43
- 239000000463 material Substances 0.000 claims abstract description 35
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 10
- 238000005804 alkylation reaction Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 230000029936 alkylation Effects 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims 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 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 2
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011363 dried mixture Substances 0.000 claims 4
- 150000002894 organic compounds Chemical class 0.000 claims 3
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 claims 2
- 150000001491 aromatic compounds Chemical class 0.000 claims 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 2
- 239000012855 volatile organic compound Substances 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002459 porosimetry Methods 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002524 electron diffraction data Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000003134 recirculating effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- -1 but not limited to Chemical compound 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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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
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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Abstract
A catalytic material includes a microporous zeolite supported on a mesoporous inorganic oxide support. The microporous zeolite can include zeolite beta, zeolite Y or ZSM-5. The mesoporous inorganic oxide can be, e.g., silica or alumina, and can optionally include other metals. Methods for making and using the catalytic material are described herein.
Description
CATALYST CONTAINING MICROPOROUS ZEOLITE IN MESOPOROUS
SUPPORT AND METHOD FOR MAKING SAME
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is a continuation-in-part of U.S. application Serial No. 09/390,276 filed September 7, 1999 to which priority is claimed, and which is herein incorporated by reference in its entirety.
BACKGROUND
1. Field of the Invention The present disclosure is related to catalyst material containing zeolite embedded in~a catalyst support, 'and particularly to a microporous zeolite embedded in a mesoporous support.
SUPPORT AND METHOD FOR MAKING SAME
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is a continuation-in-part of U.S. application Serial No. 09/390,276 filed September 7, 1999 to which priority is claimed, and which is herein incorporated by reference in its entirety.
BACKGROUND
1. Field of the Invention The present disclosure is related to catalyst material containing zeolite embedded in~a catalyst support, 'and particularly to a microporous zeolite embedded in a mesoporous support.
2. Background of the Art Most of today°s hydrocarbon processing technologies is based on'zeolite catalysts. Zeolite catalysts are well known in the art and possess well-arranged pore systems with uniform pore sizes. However, these materials tend to possess either only micropores or only~mesopores.
Micropores are defined as pores having a diameter of less than about 2 nm. Mesopores are defined as pores having a diameter ranging from about 2 nm to about 50 nm.
Because such hydrocarbon processing reactions are mass-transfer limited, a catalyst-with ideal pore size will.
facilitate transport of the reactants to active catalyst sites and transport of the products out of the catalyst.
SUMMARY OF THE INVENTION
A material useful in catalytic processing of hydrocarbons is provided herein. The material comprises a zeolite, and a porous inorganic oxide which includes at least 97 volume percent mesopores based on the micropores and mesopores of the inorganic oxide. The zeolite is preferably a microporous zeolite.such.as for'-example, zeolite beta, zeolite Y, or ZSM-5. A method for making and method for using the material are described herein.
The catalytic material described herein advantageously facilitates the transport of reactants to active catalyst sites and is about 5 times more active than the zeolite used alone.
BRIEF DESCRIPTION OF THE DRAWINGS
Various embodiments are described below with reference to the drawings wherein:
FIG. 1 is a graph showing the X-ray diffraction patterns of pure zeolite beta, mesoporous inorganic oxide support with zeolite beta (Sample 1), and an extended.
scanning time image of Sample 1;
FIG. 2 is a high resolution transmission electron microscopy image of the mesoporous inorganic oxide support with zeolite beta (Sample 1), and an inset showing an electron diffraction pattern of the zeolite .domains;
FIG. 3 is a chart showing the temperature..programmed desorption of NH3 (NH3-TPD) analysis of the niesoporous inorganic.oxide support with zeolite beta (Sample 1), and a comparison sample containing no zeolite beta;
FIG. 4 is a graph showing the mesopore size distribution of the.material produced in Examples 3, 4, and 5 herein, and of pure zeolite.beta; and FIG. 5 is a chart showing the X-ray diffraction patterns of the materials produced in Examples 2 to 5 herein, as well as pure zeolite beta.
, DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS) The catalyst described herein includes a microporous zeolite embedded in a mesoporous support. The microporous zeolite can be any type of microporous zeolite including, but not limited to, zeolite beta, zeolite Y, and ZSM-5.
Micropores are defined as pores having a diameter of less than about 2 nm. Mesopores are defined as pores having a diameter ranging from about 2 nm to about 50 nm.
Because such hydrocarbon processing reactions are mass-transfer limited, a catalyst-with ideal pore size will.
facilitate transport of the reactants to active catalyst sites and transport of the products out of the catalyst.
SUMMARY OF THE INVENTION
A material useful in catalytic processing of hydrocarbons is provided herein. The material comprises a zeolite, and a porous inorganic oxide which includes at least 97 volume percent mesopores based on the micropores and mesopores of the inorganic oxide. The zeolite is preferably a microporous zeolite.such.as for'-example, zeolite beta, zeolite Y, or ZSM-5. A method for making and method for using the material are described herein.
The catalytic material described herein advantageously facilitates the transport of reactants to active catalyst sites and is about 5 times more active than the zeolite used alone.
BRIEF DESCRIPTION OF THE DRAWINGS
Various embodiments are described below with reference to the drawings wherein:
FIG. 1 is a graph showing the X-ray diffraction patterns of pure zeolite beta, mesoporous inorganic oxide support with zeolite beta (Sample 1), and an extended.
scanning time image of Sample 1;
FIG. 2 is a high resolution transmission electron microscopy image of the mesoporous inorganic oxide support with zeolite beta (Sample 1), and an inset showing an electron diffraction pattern of the zeolite .domains;
FIG. 3 is a chart showing the temperature..programmed desorption of NH3 (NH3-TPD) analysis of the niesoporous inorganic.oxide support with zeolite beta (Sample 1), and a comparison sample containing no zeolite beta;
FIG. 4 is a graph showing the mesopore size distribution of the.material produced in Examples 3, 4, and 5 herein, and of pure zeolite.beta; and FIG. 5 is a chart showing the X-ray diffraction patterns of the materials produced in Examples 2 to 5 herein, as well as pure zeolite beta.
, DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS) The catalyst described herein includes a microporous zeolite embedded in a mesoporous support. The microporous zeolite can be any type of microporous zeolite including, but not limited to, zeolite beta, zeolite Y, and ZSM-5.
Such zeolites are known in the art and commercially available. The zeolite can be incorporated into the mesoporous support or can be synthesized in-situ in the catalyst support. ~.
The catalyst support is preferably a three dimensional mesoporous inorganic oxide material containing at least 97 volume percent mesopores (i.e., no more than 3 volume percent micropores) based on micropores and mesopores of the organic oxide material (i.e.,. without any zeolite incorporated therein), and generally at least 98 volume percent mesopores. A method for making a preferred porous silica-containing catalyst support is described in U.S.
Patent application Serial No. 09/390,276. The average mesopore size of the preferred catalyst as determined from Na-porosimetry ranges from about 2 nm to about 25 nm.
Generally, the mesoporous inorganic oxide is prepared by heating a mixture of (1) a precursor of the inorganic oxide . , in water, and (2) an organic templating agent that mixes well with the oxide precursor or the oxide species generated from the precursor, and preferably forms hydrogen bonds with it.
The starting material is generally an amorphous material and may be comprised of one or more inorganic oxides such as silicon oxide or aluminum oxide, with or without additional metal oxides. The silicon atoms may be replaced in part by metal atoms such as aluminum, titanium, vanadium, zirconium, gallium, manganese, zinc, chromium, molybdenum, nickel, cobalt awd from and the like.. The additional metals may optionally be incorporated into the mate.°ial. prior to initiating the process for producing a structure that contains mesopores. Also, after preparation of the material, cations in the system may optionally be replaced with other ions such as those of an alkali metal (e. g., sodium, potassium, lithium, etc.).
The organic templating agent is preferably a glycol (a compound that includes two or more hydroxyl groups), such as glycerol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, and the like; or ~ member(s) of the group consisting of triethanolamine, sulfolane, tetraethylene pentamine and diethylglycol dibenzoate.
The mesoporous catalyst support is a pseudo-crystalline material (i.e., no crystallinity is observed by presently available x-ray diffraction techniques). The wall thickness of the.mesopores is preferably from about 3 nm to about 25 nm. The surface area of the catalyst support as determined by BET (NZ) preferably ranges from about 400 m2/g to about 1200 m~/g. The catalyst pore volume preferably ranges from about 0.3 cm3/g to about 2.2 cm3/g.
The content of zeolite in the catalyst can range from less tham about ,lo by-weight o more than about 99o by weight, preferably from about 5o by weight to 90o b~y weight, more pref.erably.from about 20o by weight to about 80% by weight. The catalyst with zeolite included. preferably contains no more than about 5 volume percent of micropores.
More particularly, the method for making the catalyst includes suspending a zeolite in water. An inorganic oxide precursor,is then added to the water and mixed. The inorganic oxide precursor can be a silicate such as . tetraethyl orthosilicate (TEOS) or a source of aluminum such as aluminum isopropoxide: TEOS and aluminum isopropoxide are commercially available from known suppliers.
The pH of the solution is preferably kept above 7Ø
Optionally, the aqueous solution can contain other metal ions such as those indicated above. After stirring, an organic templating agent which binds to the silica (or other inorganic oxide) species by hydrogen bonding is added and mixed into the aqueous solution.' The organic templating agent helps form the mesopores during a pore-forming step, as discussed below. The organic templating agent should not be so hydrophobic so as to form a separate phase in the aqueous solution. The organic templating agent can be orie or more compound as listed above. The organic templating agent is preferably added by dropwise addition with stirring to the~ac~ueous inorganic oxide solution. After a period of time (e.g., :from about 1 to 2 hours) the mixture forms a thick gel. The w~ixture is preferably stirred during this period of time to facilitate the mixing of the components.
The solution preferably includes an alkanol, which can be added to the mixture and/s~r formed in-situ by the decomposition of the inorganic oxide precursor: For example, TEOS, upon heating, produces ethanol. Propanol may be produced by the decomposition of aluminum isopropoxide.
. The gel is then aged at a temperature of from about 5°C
to about 45°C, preferably. at room temperature, to complete the hydrolysis and poly-condensation of~the inorganic oxide source. Aging preferably can take place for up to about 48 hours, generally from about 2 hours to 30 hours, more preferably from about 10 hours.to 20 hours. After the aging step the gel is heated in air at about 98°C to 100°C for a period of time sufficient to dry the gel by driving off water~(e.g., from about 6 to about 24 hours). Preferably, the organic templating agent, which helps form the mesopores, should remain in the gel during the drying stage.
Accordingly, the preferred organic templating agent has a boiling point of at least about 150°C.
uhe dried material, which still contains the organic templating agent, is. heated to a temperature at which there is a substantial formation of mesopores. The pore-forming step is conducted at ~. temperature above the boiling point of water and up to about the boiling point of the organic templating agent. Generally, the mesopore formation is carried out at a temperature of from about 100°C to about 250°, preferably from about 150° to about 200°C. The pore-forming step can optionally be performed hydrothermally in a sealed vessel at autogenous pressure. The size of the mesopores and volume of the mesopores in the final product are influenced by the length and temperature of the.
hydrothermal step. Generally, increasing the temperature and duration of the treatment increases the percentage of mesopore volume in the final product.
After the pore-forming step the catalyst material is calcined at a temperature of from about 300°C to about 1000°C, preferably from about 400°C to about 700°C, more preferably from about 500°C to about 600°C, and maintained at the calcining temperature for a period of time sufficient to effect calcination of the material. The duration of the calcining step typically ranges from about 2 hours to about _g_ 40 hours, preferably 5 hours to 15 hours, depending, in part, upon the calcining temperature.
To prevent hot spots the temperature should be raised gradually. Preferably, the~temperature of the. catalyst material should be ramped up to the calcining temperature at a rate of from about 0.1°C/min. to about 25°C/min., more preferably from about 0.5°C/min. to about 15°C/min., and most preferably from about 1°C/min. to about 5°C/min.
During calcining the structure of the catalyst material is finally~formed while the organic molecules are expelled from the material and decomposed.
The calcination process to remove organic templating agent can be ,replaced by extraction using organic solvents, e.g.~ ethanol. In this ease the templating agent can be recovered for re-use.
Also, the catalyst powder of the present invention can be admixed with binders such as silica and/or alumina, and . , then formed into desired shapes (e. g., pellets, rings, etc.) by extrusion or other suitable methods.
Metal ions such as titanium vanadium, zirconium, gallium, manganese, zinc, 'nickel, iron, cobalt, chromium and molybdenum may be added to the catalyst by impregnation, ion exchange, or by replacing a part of the lattice atoms as described in G.W. Skeels and E.M. Flanigen in M. Occelli, et _g_ al., eds., A.C.S. Symposium Series, Vol. 398, Butterworth, pgs. 420-435 (1989).
The catalyst described herein is useful in hydrocarbon processing such~as in hirdrocracking;. hydroisomerization, dewaxing, alkylation, and the like.
For example, alkylation of hydrocarbons with olefins employing catalyst described herein -can be performed at a temperature of from about 90° C to about 250° C, a pressure of from about 10 psig to about 500 psig, and a space velocity of from about 1 WHSV to about 20 WHSV.
Hydrocracking of hydrocarbons employing the catalyst described herein can be performed under reaction conditions including a temperature of from about 200°C to about 400° C, a pressure of from about 150 psig to about 1,000 prig, and a space velocity of from about 1 WHSV to about 50 WHSV.
Hydroisomerization of hydrocarbons employing the catalyst described herein can be performed under reaction conditions including a temperature of from about 150°C to about 500°C a pressure of from about 15 psig to about 3500 psig, and a space velocity of from about 0.1 WHSV to about 20 WHSV.
Catalytic dewaxing of hydrocarbons employing the catalyst described herein can be performed under reaction conditions including a temperature of from about 150°C to about 500° C, a pressure of from about 100 psig to about 1,500 psig, and a space velocity of from about 0.1 WHSV to about 20 WHSV.
The method of making the catalyst composition of the ~ present invention is illustrated by the Examples 1-5 given below. Example 6 illustrates the use.of. the catalyst in an alkylation process. Comparative Example A illustra..tes the use of pure zeolite beta without the mesoporou~s support described herein and is not in accordance with the present invention. Composition amounts are given in parts by weight.
First, 1.48 parts calcined zeolite beta with an Si/A1 ratio of 24.9 and an average particle size of 1 um were suspended in 16.32 parts water and stirred for 30 minutes.
Then 20.32 parts tetraethylorthosilicate (TEOS) were added to the suspension with stirring. After continuous stirring for another 30 minutes, 9.33 parts triethanolamine were added. After stirring again for another 30 minutes, 4.02 parts tetraethylammonium hydroxide aqueous solution (35~
solution available from Aldrich) were added drop-wise to the mixture to increase the pH. After stirring for about 2 hours, the mixture formed a thick non-flowing gel.~~ This gel was aged at room temperature under static conditions for 17 hours. Next, the gel was dried in air at 100°C for 28 hours. The dried gel was transferred into an autoclave and hydrothermally treated at 170°C for~17.5 hours.. Finally, it 5~ was calcined at 600° for 10 hours in air with ~a ramp rate of 1°C/min.
The final product was designated as Sample 1. The theoretical amount of zeolite beta present in the Sample 1 was 20wt%. Sample 1 was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen porosimetry, argon porosimetry and NH3-temperature programmed desorption (TPD). Pure zeolite beta was also characterized by XRD for purposes of comparison.
Referring to FIG.~1, the.XRD pattern of the pure zeolite beta, depicted in plot "b", shows the most pronounced characteristic reflections at about 7.7° and 22.2° in 2 theta (33 minute scanning time). The XRD pattern of the mesoporous inorganic oxide support with the zeolite beta crystals (Sample 1) is depicted in plot "a". An intense peak at low angle is observed, indicating that Sample 1 is a meso-structured~material. The peaks for beta zeolite are relatively small because the maximum theoretical zeolite content of the final product is only about 20 wt%.
When the scanning time for Sample 1 was extended to 45 hours, the characteristic peaks of zeolite beta become clearly visible, as depicted in plot "c".
Referring now to FIG. 2, a high resolution transmission electron~microscopy image "TEM" of Sample 1 is depicted, which~shows dark~gray domains ll in a mesoporous matrix 12.
The inset "ED" depicts an electron diffraction pattern which confirms that the dark gray domains 11 are beta zeolitE
crystals.
Nitrogen adsorption shows that Sample 1 has a narrow mesopore size distribution, mainly centered at about 9.0 nm, high surface area of 710 m~lg and high total pore volume of 1.01 cm3/g. Argon adsorption shows a peak of micropore size distribution around about 0.64 nm, corresponding to micropore size in zeolite beta. The micropore volume of pores with a diameter smaller than 0.7 nm was 0.04 cm3.
This is about 16% of the micropore volume of the pure zeolite beta. Initial addition of uncalcined zeolite beta -, was 20 wt.% based on the final composite. The used zeolite beta lost about 20 wt.% due to the removal of template during calcination. Taking the mass loss of zeolite during calcination into account, the expected content of zeolite beta in the final composite is about 16 wt.%, which is consistent with the value obtained from micropore volume.
Referring to FIG. 3, the NH3-TPD measurement of Sample 1 showed two desorption peaks, indicating that there are strong acid sites similar to those in zeolites.
First, 3.40 parts calcined zeolite beta with an Si/A1 ratio of 150 and an average particle size of 0.2 um were suspended in 84.98 parts water and stirred for 30 minutes.
Then 105.80 parts TEOS were added to the suspension with stirring. After continuous stirring for another 30 minutes, 38.27 parts triethanolamine were added. After stirring again for another 30 minutes, 20.93 parts tetraethylammonium hydroxide aqueous solution (35%) were added drop-wise to the mixture. After stirring for about 2 hours the mixture turned into a thick non-flowing gel. This gel was aged at room temperature under static conditions for 24 hours.
Next, the gel was dried in air at 98-100°C for 24 hours.
y The dried gel was transferred into four 50 ml autoclaves and hydrothermally treated at 180°C for 4 hours. Finally, it was calcined at 600°C for 10 hours in air with a ramp rate of 1°C/min. The XRD pattern of the resultant product, designated as Sample 2, is shown in FIG. 5. There is about 10 wt.% zeolite beta in the final composite.
First, 4.59.parts calcined zeolite beta with an Si/A1 ratio of 150 and an average partic).e size of 0.2 ~::~ were suspended in 51.02 parts water and stirred for 30 minutes.
Then 22.97 parts triethanolamine were added to the suspension with stirring. After continuous stirring for another 30 minutes, 63.50 parts TEOS were added. After stirring again for another 30 minutes, 12.58 parts tetraethylammonium hydroxide aqueous solution -(35%) were added drop-wise to the mixture. After stirring for about 2 hours, the mixture formed a thick non-flowing gel. This gel was aged at room temperature under static conditions for 24 hours. Next, the gel was dried in air at 100°C for 24 hours. The dried gel was transferred into three 50 m1 autoclaves and hydrothermally treated at 1.80°C for 4 hours.
Finally, it was calcined at 60.0°C for 10 hours in air with a ramp rate of 1°C/min. The XRD pattern of the resultant product, designated as Sample 3, is shown in FIG. 5, which clearly shows two characteristic peaks of zeolite beta.
There is about 20 wt.% zeolite beta.in the final composite.
Nitrogen adsorption revealed its surface area of about 730 m2/g, pore volume of about 1.08 cm3/g. Its mesopore size distribution is shown in FIG. 4.
First, 12.23 parts calci,ned zeolite beta with an Si/Al ratio of 150 and an average particle size of 0.2 um were suspended in 50.99 parts water and stirred for 30 minutes.
Then 22.96 parts triethanolamine were added to the suspension with stirring. After continuous stirring for another 30 minutes, 63.48 parts TEOS were added. After stirring again for another 30 minutes, 12.68 parts tetraethylammonium hydroxide aqueous solution (35%) were added drop-wise to the mixture. After stirring for about 2 hours, the mixture formed a thick non-flowing gel. This gel was aged at room temperature under static conditions for 24 hours. Next, the gel was dried in air at 100°C for 24 hours. The dried gel was transferred into three'50 ml autoclaves and hydrothermally treated at 180°C for 4 hours.
Finally, it was calcined at 600°C for 10 hours in air with a ramp rate of 1°C/min. The XRD pattern of the resultant product, designated as Sample 4, is shown in FIG. 5, which clearly shows two characteristic peaks of zeolite beta.
There is about 20 wt.~ zeolite beta in the final composite.
Nitrogen adsorption revealed its surface area of about 637 m~/g, pore volume of about 1.07 cm3/g. Its mesopore size distribution is shown in FIG. 4.
First, 9.17 parts calcined zeolite beta with an Si/A1 ratio of 150 and an average particle size of 0.~ um were suspended in 16.99 parts water and stirred for 30 minutes.
Then 7.65 parts triethanolamine were added to the above sospension,under stirring. After continuous stirring for another 30 minutes, 21.16 parts TEOS were added. After stirring again for another 30 minutes, 4.19 parts tetraethylammonium hydroxide aqueous solution =(35%) were added drop-wise to the mixture. After stirring for about 2 hours, th.e mixture formed a thick non-flowing gel. This gel was aged at room temperature under static conditions for 24 hours. Next, the gel was dried in air at 100°C for 24 hours. The dried gel was transferred into three 50 ml autoclaves and hydrothermally treated at 180°C for 4 hours.
Finally, it was calcined at 600°C for 10 hours in air with a ramp rate of 1°C/min. The XRD pattern of the resultant -, , product, designated as Sample 5, is shown in FIG. S, which clearly shows two characteristic peaks of zeolite beta.
There is about 60 wt.% zeolite beta in the final composite.
Nitrogen adsorption revealed its surface area of about 639 m2/g, pore volume of about 0.97 cm3/g. Its mesopore size distribution is shown in FIG. 4.
Eight parts of Sample 1 were mixed with two parts of alumina in the form of Nyacol to~provide a catalyst. The mixture was dried and calc,ined by raising the temperature to 120°C at the rate of 5°C/min, maintaining the 120°C
temperature for one hour, then raising the temperature at the rate of 5°C/min to 500°C for five hours and finally lowering the temperature at the rate of 5°C/min to 150°C and then allowing the catalyst to cool to room temperature in a desiccator. The catalyst was then manually crushed and sieved to.-12/+20 mesh for activity testing. This catalyst contained 16 wt.o zeolite beta in mesoporous support. A
recirculating differential fixed-bed bed reactor was charged with 1.000 gram of catalyst. The recirculating rate (200 gm/min) was about 33 times the feed rate (6.1 gm/min). The loaded reactor was initially filled with benzene, the feed (benzene containing 0.35 wt.~ ethylene) was metered in with -- a metering pump when the reactor reached 190°C. The run was carried out for seven hours. The reaction conditions included a temperature of 190°C a pressure of 350 psig and a space velocity of 6 WHSV. Feed samples were taken at the beginning, the middle and the end of the run. Product samples were taken every third minute and analyzed by gas chromatography. Based on the rate equation, a rate constant of 0.30 cm3/g-sec was obtained for the alkylation of benzene with ethylene to form ethylbenzene'for 16 wt.%~zeolite beta-containing catalyst. Alternatively, this value is equivalent: ofya value of 1.50 cm3/g-sec for. a 80 wt. o of zeolite beta-containing catalyst.
COMPARISON SAMPLE A
An all silica mesoporous support was made in accordance with the method described in Example 1 except that ,no zeolite was incorporated. The resulting support was designated as Comparison Sample A. An NH3-TPD measurement was made of Comparison Sample A and the resulting measurement is depicted in. FIG. 3. , a~=-:.
COMPARISON EXAMPLE B
A sample of zeolite beta obtained from a commercial supplier and containing 80 wt.°s zeolite beta (Si/Al ratio of 4.9) and 20o binder was resized to -12/+20 mesh. The pore size distribution of zeolite beta is depicted in FIG. 4.
The activity of the pure zeolite beta of this Comparison Example was tested in the same alkylation reaction using the same methodology and apparatus described in Example 6 above.
A rate constant of 0.29 cm3/g-sec was obtained.
Comparing the results of Example 6 with Comparison Example B, the catalyst of Example 6, which is in accordance with the present invention, has about five times greater activity than an equivalent amount of zeo.lite beta alone for ~ the alkylation of benzene with ethylene. These results indicate that the integrity of the zeolite crystals in the mesoporous catalyst~support is.maintained during the synthesis of Sample 1. The results also demonstrate that the microporous zeolite beta in the mesoporous support of Sample 1 wa.s still accessible after the synthesis of the catalyst ~~nd that the mesopores of the support facilitate mass transfer in aromatic alkylation reactions.
While the above description contains many specifics, these specifics should not be construed as limitations on the scope of the invention, but merely as exemplifications of preferred embodiments thereof. Those skilled in, the art will envision many other possibilities within .the scope and spirit of the invention as defined by the claims appended hereto.
The catalyst support is preferably a three dimensional mesoporous inorganic oxide material containing at least 97 volume percent mesopores (i.e., no more than 3 volume percent micropores) based on micropores and mesopores of the organic oxide material (i.e.,. without any zeolite incorporated therein), and generally at least 98 volume percent mesopores. A method for making a preferred porous silica-containing catalyst support is described in U.S.
Patent application Serial No. 09/390,276. The average mesopore size of the preferred catalyst as determined from Na-porosimetry ranges from about 2 nm to about 25 nm.
Generally, the mesoporous inorganic oxide is prepared by heating a mixture of (1) a precursor of the inorganic oxide . , in water, and (2) an organic templating agent that mixes well with the oxide precursor or the oxide species generated from the precursor, and preferably forms hydrogen bonds with it.
The starting material is generally an amorphous material and may be comprised of one or more inorganic oxides such as silicon oxide or aluminum oxide, with or without additional metal oxides. The silicon atoms may be replaced in part by metal atoms such as aluminum, titanium, vanadium, zirconium, gallium, manganese, zinc, chromium, molybdenum, nickel, cobalt awd from and the like.. The additional metals may optionally be incorporated into the mate.°ial. prior to initiating the process for producing a structure that contains mesopores. Also, after preparation of the material, cations in the system may optionally be replaced with other ions such as those of an alkali metal (e. g., sodium, potassium, lithium, etc.).
The organic templating agent is preferably a glycol (a compound that includes two or more hydroxyl groups), such as glycerol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, and the like; or ~ member(s) of the group consisting of triethanolamine, sulfolane, tetraethylene pentamine and diethylglycol dibenzoate.
The mesoporous catalyst support is a pseudo-crystalline material (i.e., no crystallinity is observed by presently available x-ray diffraction techniques). The wall thickness of the.mesopores is preferably from about 3 nm to about 25 nm. The surface area of the catalyst support as determined by BET (NZ) preferably ranges from about 400 m2/g to about 1200 m~/g. The catalyst pore volume preferably ranges from about 0.3 cm3/g to about 2.2 cm3/g.
The content of zeolite in the catalyst can range from less tham about ,lo by-weight o more than about 99o by weight, preferably from about 5o by weight to 90o b~y weight, more pref.erably.from about 20o by weight to about 80% by weight. The catalyst with zeolite included. preferably contains no more than about 5 volume percent of micropores.
More particularly, the method for making the catalyst includes suspending a zeolite in water. An inorganic oxide precursor,is then added to the water and mixed. The inorganic oxide precursor can be a silicate such as . tetraethyl orthosilicate (TEOS) or a source of aluminum such as aluminum isopropoxide: TEOS and aluminum isopropoxide are commercially available from known suppliers.
The pH of the solution is preferably kept above 7Ø
Optionally, the aqueous solution can contain other metal ions such as those indicated above. After stirring, an organic templating agent which binds to the silica (or other inorganic oxide) species by hydrogen bonding is added and mixed into the aqueous solution.' The organic templating agent helps form the mesopores during a pore-forming step, as discussed below. The organic templating agent should not be so hydrophobic so as to form a separate phase in the aqueous solution. The organic templating agent can be orie or more compound as listed above. The organic templating agent is preferably added by dropwise addition with stirring to the~ac~ueous inorganic oxide solution. After a period of time (e.g., :from about 1 to 2 hours) the mixture forms a thick gel. The w~ixture is preferably stirred during this period of time to facilitate the mixing of the components.
The solution preferably includes an alkanol, which can be added to the mixture and/s~r formed in-situ by the decomposition of the inorganic oxide precursor: For example, TEOS, upon heating, produces ethanol. Propanol may be produced by the decomposition of aluminum isopropoxide.
. The gel is then aged at a temperature of from about 5°C
to about 45°C, preferably. at room temperature, to complete the hydrolysis and poly-condensation of~the inorganic oxide source. Aging preferably can take place for up to about 48 hours, generally from about 2 hours to 30 hours, more preferably from about 10 hours.to 20 hours. After the aging step the gel is heated in air at about 98°C to 100°C for a period of time sufficient to dry the gel by driving off water~(e.g., from about 6 to about 24 hours). Preferably, the organic templating agent, which helps form the mesopores, should remain in the gel during the drying stage.
Accordingly, the preferred organic templating agent has a boiling point of at least about 150°C.
uhe dried material, which still contains the organic templating agent, is. heated to a temperature at which there is a substantial formation of mesopores. The pore-forming step is conducted at ~. temperature above the boiling point of water and up to about the boiling point of the organic templating agent. Generally, the mesopore formation is carried out at a temperature of from about 100°C to about 250°, preferably from about 150° to about 200°C. The pore-forming step can optionally be performed hydrothermally in a sealed vessel at autogenous pressure. The size of the mesopores and volume of the mesopores in the final product are influenced by the length and temperature of the.
hydrothermal step. Generally, increasing the temperature and duration of the treatment increases the percentage of mesopore volume in the final product.
After the pore-forming step the catalyst material is calcined at a temperature of from about 300°C to about 1000°C, preferably from about 400°C to about 700°C, more preferably from about 500°C to about 600°C, and maintained at the calcining temperature for a period of time sufficient to effect calcination of the material. The duration of the calcining step typically ranges from about 2 hours to about _g_ 40 hours, preferably 5 hours to 15 hours, depending, in part, upon the calcining temperature.
To prevent hot spots the temperature should be raised gradually. Preferably, the~temperature of the. catalyst material should be ramped up to the calcining temperature at a rate of from about 0.1°C/min. to about 25°C/min., more preferably from about 0.5°C/min. to about 15°C/min., and most preferably from about 1°C/min. to about 5°C/min.
During calcining the structure of the catalyst material is finally~formed while the organic molecules are expelled from the material and decomposed.
The calcination process to remove organic templating agent can be ,replaced by extraction using organic solvents, e.g.~ ethanol. In this ease the templating agent can be recovered for re-use.
Also, the catalyst powder of the present invention can be admixed with binders such as silica and/or alumina, and . , then formed into desired shapes (e. g., pellets, rings, etc.) by extrusion or other suitable methods.
Metal ions such as titanium vanadium, zirconium, gallium, manganese, zinc, 'nickel, iron, cobalt, chromium and molybdenum may be added to the catalyst by impregnation, ion exchange, or by replacing a part of the lattice atoms as described in G.W. Skeels and E.M. Flanigen in M. Occelli, et _g_ al., eds., A.C.S. Symposium Series, Vol. 398, Butterworth, pgs. 420-435 (1989).
The catalyst described herein is useful in hydrocarbon processing such~as in hirdrocracking;. hydroisomerization, dewaxing, alkylation, and the like.
For example, alkylation of hydrocarbons with olefins employing catalyst described herein -can be performed at a temperature of from about 90° C to about 250° C, a pressure of from about 10 psig to about 500 psig, and a space velocity of from about 1 WHSV to about 20 WHSV.
Hydrocracking of hydrocarbons employing the catalyst described herein can be performed under reaction conditions including a temperature of from about 200°C to about 400° C, a pressure of from about 150 psig to about 1,000 prig, and a space velocity of from about 1 WHSV to about 50 WHSV.
Hydroisomerization of hydrocarbons employing the catalyst described herein can be performed under reaction conditions including a temperature of from about 150°C to about 500°C a pressure of from about 15 psig to about 3500 psig, and a space velocity of from about 0.1 WHSV to about 20 WHSV.
Catalytic dewaxing of hydrocarbons employing the catalyst described herein can be performed under reaction conditions including a temperature of from about 150°C to about 500° C, a pressure of from about 100 psig to about 1,500 psig, and a space velocity of from about 0.1 WHSV to about 20 WHSV.
The method of making the catalyst composition of the ~ present invention is illustrated by the Examples 1-5 given below. Example 6 illustrates the use.of. the catalyst in an alkylation process. Comparative Example A illustra..tes the use of pure zeolite beta without the mesoporou~s support described herein and is not in accordance with the present invention. Composition amounts are given in parts by weight.
First, 1.48 parts calcined zeolite beta with an Si/A1 ratio of 24.9 and an average particle size of 1 um were suspended in 16.32 parts water and stirred for 30 minutes.
Then 20.32 parts tetraethylorthosilicate (TEOS) were added to the suspension with stirring. After continuous stirring for another 30 minutes, 9.33 parts triethanolamine were added. After stirring again for another 30 minutes, 4.02 parts tetraethylammonium hydroxide aqueous solution (35~
solution available from Aldrich) were added drop-wise to the mixture to increase the pH. After stirring for about 2 hours, the mixture formed a thick non-flowing gel.~~ This gel was aged at room temperature under static conditions for 17 hours. Next, the gel was dried in air at 100°C for 28 hours. The dried gel was transferred into an autoclave and hydrothermally treated at 170°C for~17.5 hours.. Finally, it 5~ was calcined at 600° for 10 hours in air with ~a ramp rate of 1°C/min.
The final product was designated as Sample 1. The theoretical amount of zeolite beta present in the Sample 1 was 20wt%. Sample 1 was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen porosimetry, argon porosimetry and NH3-temperature programmed desorption (TPD). Pure zeolite beta was also characterized by XRD for purposes of comparison.
Referring to FIG.~1, the.XRD pattern of the pure zeolite beta, depicted in plot "b", shows the most pronounced characteristic reflections at about 7.7° and 22.2° in 2 theta (33 minute scanning time). The XRD pattern of the mesoporous inorganic oxide support with the zeolite beta crystals (Sample 1) is depicted in plot "a". An intense peak at low angle is observed, indicating that Sample 1 is a meso-structured~material. The peaks for beta zeolite are relatively small because the maximum theoretical zeolite content of the final product is only about 20 wt%.
When the scanning time for Sample 1 was extended to 45 hours, the characteristic peaks of zeolite beta become clearly visible, as depicted in plot "c".
Referring now to FIG. 2, a high resolution transmission electron~microscopy image "TEM" of Sample 1 is depicted, which~shows dark~gray domains ll in a mesoporous matrix 12.
The inset "ED" depicts an electron diffraction pattern which confirms that the dark gray domains 11 are beta zeolitE
crystals.
Nitrogen adsorption shows that Sample 1 has a narrow mesopore size distribution, mainly centered at about 9.0 nm, high surface area of 710 m~lg and high total pore volume of 1.01 cm3/g. Argon adsorption shows a peak of micropore size distribution around about 0.64 nm, corresponding to micropore size in zeolite beta. The micropore volume of pores with a diameter smaller than 0.7 nm was 0.04 cm3.
This is about 16% of the micropore volume of the pure zeolite beta. Initial addition of uncalcined zeolite beta -, was 20 wt.% based on the final composite. The used zeolite beta lost about 20 wt.% due to the removal of template during calcination. Taking the mass loss of zeolite during calcination into account, the expected content of zeolite beta in the final composite is about 16 wt.%, which is consistent with the value obtained from micropore volume.
Referring to FIG. 3, the NH3-TPD measurement of Sample 1 showed two desorption peaks, indicating that there are strong acid sites similar to those in zeolites.
First, 3.40 parts calcined zeolite beta with an Si/A1 ratio of 150 and an average particle size of 0.2 um were suspended in 84.98 parts water and stirred for 30 minutes.
Then 105.80 parts TEOS were added to the suspension with stirring. After continuous stirring for another 30 minutes, 38.27 parts triethanolamine were added. After stirring again for another 30 minutes, 20.93 parts tetraethylammonium hydroxide aqueous solution (35%) were added drop-wise to the mixture. After stirring for about 2 hours the mixture turned into a thick non-flowing gel. This gel was aged at room temperature under static conditions for 24 hours.
Next, the gel was dried in air at 98-100°C for 24 hours.
y The dried gel was transferred into four 50 ml autoclaves and hydrothermally treated at 180°C for 4 hours. Finally, it was calcined at 600°C for 10 hours in air with a ramp rate of 1°C/min. The XRD pattern of the resultant product, designated as Sample 2, is shown in FIG. 5. There is about 10 wt.% zeolite beta in the final composite.
First, 4.59.parts calcined zeolite beta with an Si/A1 ratio of 150 and an average partic).e size of 0.2 ~::~ were suspended in 51.02 parts water and stirred for 30 minutes.
Then 22.97 parts triethanolamine were added to the suspension with stirring. After continuous stirring for another 30 minutes, 63.50 parts TEOS were added. After stirring again for another 30 minutes, 12.58 parts tetraethylammonium hydroxide aqueous solution -(35%) were added drop-wise to the mixture. After stirring for about 2 hours, the mixture formed a thick non-flowing gel. This gel was aged at room temperature under static conditions for 24 hours. Next, the gel was dried in air at 100°C for 24 hours. The dried gel was transferred into three 50 m1 autoclaves and hydrothermally treated at 1.80°C for 4 hours.
Finally, it was calcined at 60.0°C for 10 hours in air with a ramp rate of 1°C/min. The XRD pattern of the resultant product, designated as Sample 3, is shown in FIG. 5, which clearly shows two characteristic peaks of zeolite beta.
There is about 20 wt.% zeolite beta.in the final composite.
Nitrogen adsorption revealed its surface area of about 730 m2/g, pore volume of about 1.08 cm3/g. Its mesopore size distribution is shown in FIG. 4.
First, 12.23 parts calci,ned zeolite beta with an Si/Al ratio of 150 and an average particle size of 0.2 um were suspended in 50.99 parts water and stirred for 30 minutes.
Then 22.96 parts triethanolamine were added to the suspension with stirring. After continuous stirring for another 30 minutes, 63.48 parts TEOS were added. After stirring again for another 30 minutes, 12.68 parts tetraethylammonium hydroxide aqueous solution (35%) were added drop-wise to the mixture. After stirring for about 2 hours, the mixture formed a thick non-flowing gel. This gel was aged at room temperature under static conditions for 24 hours. Next, the gel was dried in air at 100°C for 24 hours. The dried gel was transferred into three'50 ml autoclaves and hydrothermally treated at 180°C for 4 hours.
Finally, it was calcined at 600°C for 10 hours in air with a ramp rate of 1°C/min. The XRD pattern of the resultant product, designated as Sample 4, is shown in FIG. 5, which clearly shows two characteristic peaks of zeolite beta.
There is about 20 wt.~ zeolite beta in the final composite.
Nitrogen adsorption revealed its surface area of about 637 m~/g, pore volume of about 1.07 cm3/g. Its mesopore size distribution is shown in FIG. 4.
First, 9.17 parts calcined zeolite beta with an Si/A1 ratio of 150 and an average particle size of 0.~ um were suspended in 16.99 parts water and stirred for 30 minutes.
Then 7.65 parts triethanolamine were added to the above sospension,under stirring. After continuous stirring for another 30 minutes, 21.16 parts TEOS were added. After stirring again for another 30 minutes, 4.19 parts tetraethylammonium hydroxide aqueous solution =(35%) were added drop-wise to the mixture. After stirring for about 2 hours, th.e mixture formed a thick non-flowing gel. This gel was aged at room temperature under static conditions for 24 hours. Next, the gel was dried in air at 100°C for 24 hours. The dried gel was transferred into three 50 ml autoclaves and hydrothermally treated at 180°C for 4 hours.
Finally, it was calcined at 600°C for 10 hours in air with a ramp rate of 1°C/min. The XRD pattern of the resultant -, , product, designated as Sample 5, is shown in FIG. S, which clearly shows two characteristic peaks of zeolite beta.
There is about 60 wt.% zeolite beta in the final composite.
Nitrogen adsorption revealed its surface area of about 639 m2/g, pore volume of about 0.97 cm3/g. Its mesopore size distribution is shown in FIG. 4.
Eight parts of Sample 1 were mixed with two parts of alumina in the form of Nyacol to~provide a catalyst. The mixture was dried and calc,ined by raising the temperature to 120°C at the rate of 5°C/min, maintaining the 120°C
temperature for one hour, then raising the temperature at the rate of 5°C/min to 500°C for five hours and finally lowering the temperature at the rate of 5°C/min to 150°C and then allowing the catalyst to cool to room temperature in a desiccator. The catalyst was then manually crushed and sieved to.-12/+20 mesh for activity testing. This catalyst contained 16 wt.o zeolite beta in mesoporous support. A
recirculating differential fixed-bed bed reactor was charged with 1.000 gram of catalyst. The recirculating rate (200 gm/min) was about 33 times the feed rate (6.1 gm/min). The loaded reactor was initially filled with benzene, the feed (benzene containing 0.35 wt.~ ethylene) was metered in with -- a metering pump when the reactor reached 190°C. The run was carried out for seven hours. The reaction conditions included a temperature of 190°C a pressure of 350 psig and a space velocity of 6 WHSV. Feed samples were taken at the beginning, the middle and the end of the run. Product samples were taken every third minute and analyzed by gas chromatography. Based on the rate equation, a rate constant of 0.30 cm3/g-sec was obtained for the alkylation of benzene with ethylene to form ethylbenzene'for 16 wt.%~zeolite beta-containing catalyst. Alternatively, this value is equivalent: ofya value of 1.50 cm3/g-sec for. a 80 wt. o of zeolite beta-containing catalyst.
COMPARISON SAMPLE A
An all silica mesoporous support was made in accordance with the method described in Example 1 except that ,no zeolite was incorporated. The resulting support was designated as Comparison Sample A. An NH3-TPD measurement was made of Comparison Sample A and the resulting measurement is depicted in. FIG. 3. , a~=-:.
COMPARISON EXAMPLE B
A sample of zeolite beta obtained from a commercial supplier and containing 80 wt.°s zeolite beta (Si/Al ratio of 4.9) and 20o binder was resized to -12/+20 mesh. The pore size distribution of zeolite beta is depicted in FIG. 4.
The activity of the pure zeolite beta of this Comparison Example was tested in the same alkylation reaction using the same methodology and apparatus described in Example 6 above.
A rate constant of 0.29 cm3/g-sec was obtained.
Comparing the results of Example 6 with Comparison Example B, the catalyst of Example 6, which is in accordance with the present invention, has about five times greater activity than an equivalent amount of zeo.lite beta alone for ~ the alkylation of benzene with ethylene. These results indicate that the integrity of the zeolite crystals in the mesoporous catalyst~support is.maintained during the synthesis of Sample 1. The results also demonstrate that the microporous zeolite beta in the mesoporous support of Sample 1 wa.s still accessible after the synthesis of the catalyst ~~nd that the mesopores of the support facilitate mass transfer in aromatic alkylation reactions.
While the above description contains many specifics, these specifics should not be construed as limitations on the scope of the invention, but merely as exemplifications of preferred embodiments thereof. Those skilled in, the art will envision many other possibilities within .the scope and spirit of the invention as defined by the claims appended hereto.
Claims (31)
1. A material which comprises:
a zeolite; and, a porous inorganic oxide which includes at least 97 volume percent mesopores based on micropores and mesopores of the inorganic oxide.
a zeolite; and, a porous inorganic oxide which includes at least 97 volume percent mesopores based on micropores and mesopores of the inorganic oxide.
2. The material of claim 1 wherein the zeolite is a microporous zeolite.
3. The material of claim 2 wherein the microporous zeolite is selected from the group consisting of zeolite beta, zeolite Y and ZSM-5.
4. The material of claim 1 wherein the porous inorganic oxide contains at least 98 volume percent mesopores.
5. The material of claim 1 wherein the mesopores have a size ranging from about 2 nm to about 25 nm.
6. The material of claim 1 wherein the porous inorganic oxide is silicon oxide.
7. The material of claim 1 wherein the porous inorganic oxide is aluminum oxide.
8. The material of claim 1 including metal atoms selected from the group consisting of aluminum, titanium, vanadium, zirconium, gallium, manganese, zinc, chromium, molybdenum, nickel, cobalt and iron.
9. The material of claim 1 wherein the composition percentage by weight of the zeolite ranges from about 5% to about 90%.
10. The material of claim 1 wherein the composition percentage by weight of the zeolite ranges from about 20% to about 80%.
11. A method for making a catalytic material which comprises the steps of:
a) combining a zeolite with water, an inorganic oxide or a precursor of an inorganic oxide, and at least one mesopore forming organic compound that binds to the inorganic oxide or the precursor of the inorganic oxide by hydrogen bonding to form a mixture;
b) drying the mixture;
c) heating the dried mixture to a temperature and for a period of time sufficient to form a mesoporous oxide structure.
a) combining a zeolite with water, an inorganic oxide or a precursor of an inorganic oxide, and at least one mesopore forming organic compound that binds to the inorganic oxide or the precursor of the inorganic oxide by hydrogen bonding to form a mixture;
b) drying the mixture;
c) heating the dried mixture to a temperature and for a period of time sufficient to form a mesoporous oxide structure.
12. The method of claim 11 wherein said mesopore forming organic compound is selected from the group consisting of glycerol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, triethanolamine, sulfolane, tetraethylene pentamine and diethylene glycol dibenzoate.
13. The method of claim 11 wherein said mesopore forming organic compound has a boiling point of at least about 150°C.
14. The method of claim 11 wherein the inorganic oxide is formed by reacting an inorganic oxide precursor with the water.
15. The method of claim 14 wherein the inorganic oxide precursor is selected from the group consisting of tetraethyl orthosilicate and aluminum isopropoxide.
16. The method of claim 11 wherein the mixture is maintained at a pH above about 7Ø
17. The method of claim 11 wherein the compound is added to the mixture by dropwise addition with stirring and wherein the mixture forms a gel.
18. The method of claim 11 wherein the mixture includes an alkanol.
19. The method of claim 11 wherein the mixture is dried by heating in air at a temperature and for a period of time sufficient to drive off water and volatile organic compounds.
20. The method of claim 11 wherein the heating step (c) comprises heating the dried mixture to a temperature of from about 100°C to about 250°C.
21. The method of claim 11 wherein the heating step (c) comprises heating the dried material to a temperature of from about 150°C to about 200°C.
22. The method of claim 11 further comprising the step of calcining the heated dried mixture at a temperature of from about 300°C to about 1000°C.
23. The method of claim 11 further including the step of calcining the heated dried mixture at a temperature of from about 400°C to about 700°C for about 2 hours to about 40 hours.
24. The method of claim 11 further comprising combining metal ions with the mixture, the metal being selected from the group consisting of titanium, vanadium, zirconium, gallium, manganese, zinc, nickel, iron, cobalt, chromium and molybdenum.
25. The method of claim 11 further comprising the steps of admixing a binder with the catalytic material and forming the catalytic material into a predetermined shape.
26. A process for treating a hydrocarbon feed comprising:
contacting a feed containing at least one hydrocarbon component with a catalytically effective amount of a catalyst which includes a zeolite supported on a porous inorganic oxide having at least 97 volume percent mesopores based on micropores and mesopores of the porous inorganic oxide under reaction conditions sufficient to effect conversion of said hydrocarbon component.
contacting a feed containing at least one hydrocarbon component with a catalytically effective amount of a catalyst which includes a zeolite supported on a porous inorganic oxide having at least 97 volume percent mesopores based on micropores and mesopores of the porous inorganic oxide under reaction conditions sufficient to effect conversion of said hydrocarbon component.
27. The process of claim 26 wherein the conversion of the hydrocarbon component is effected by means of a hydrocracking reaction hydroisomerization reaction, dewaxing reaction, or alkylation reaction.
28. The process of claim 26 wherein said feed includes an aromatic compound and an olefin and the reaction conditions are sufficient to effect alkylation of the aromatic compound with the olefin.
29. The process of claim 28 wherein the reaction conditions include a temperature of from about 90°C to about 250°, a pressure of from about 10 psig to about 500 psig, and a space velocity of from about 1 WHSV to about 20 WHSV.
30. The process of claim 26 wherein the zeolite is a microporous zeolite.
31. The process of claim 30 wherein the microporous zeolite is zeolite beta.
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US09/995,227 US6762143B2 (en) | 1999-09-07 | 2001-11-27 | Catalyst containing microporous zeolite in mesoporous support |
PCT/US2002/036912 WO2003045548A1 (en) | 2001-11-27 | 2002-11-18 | Catalyst containing microporous zeolite in mesoporous support and method for making same |
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BR0013787B1 (en) | 1999-09-07 | 2010-11-16 | process for producing an inorganic oxide containing micro and mesoporous. | |
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2001
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2002
- 2002-11-18 WO PCT/US2002/036912 patent/WO2003045548A1/en active Application Filing
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- 2002-11-18 JP JP2003547042A patent/JP2005510345A/en active Pending
- 2002-11-18 CN CNA028235576A patent/CN1596150A/en active Pending
- 2002-11-18 EP EP02784491A patent/EP1453603A1/en not_active Withdrawn
- 2002-11-18 CA CA002468328A patent/CA2468328A1/en not_active Abandoned
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IN2004MU00706A (en) | 2005-11-18 |
MXPA04004987A (en) | 2004-08-11 |
US20050013773A1 (en) | 2005-01-20 |
IN224393B (en) | 2009-01-09 |
US6930217B2 (en) | 2005-08-16 |
US20020074263A1 (en) | 2002-06-20 |
WO2003045548A1 (en) | 2003-06-05 |
EP1453603A1 (en) | 2004-09-08 |
US6762143B2 (en) | 2004-07-13 |
MY122929A (en) | 2006-05-31 |
AU2002346427A1 (en) | 2003-06-10 |
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