JP7130666B2 - 高活性、高ガソリン収率、および低コークスの流動接触分解触媒 - Google Patents
高活性、高ガソリン収率、および低コークスの流動接触分解触媒 Download PDFInfo
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- JP7130666B2 JP7130666B2 JP2019555909A JP2019555909A JP7130666B2 JP 7130666 B2 JP7130666 B2 JP 7130666B2 JP 2019555909 A JP2019555909 A JP 2019555909A JP 2019555909 A JP2019555909 A JP 2019555909A JP 7130666 B2 JP7130666 B2 JP 7130666B2
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- zeolite
- catalyst
- alumina
- flash
- zsm
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- 239000003054 catalyst Substances 0.000 title claims description 109
- 238000004231 fluid catalytic cracking Methods 0.000 title claims description 68
- 239000000571 coke Substances 0.000 title description 15
- 239000003502 gasoline Substances 0.000 title description 12
- 230000000694 effects Effects 0.000 title 1
- 239000010457 zeolite Substances 0.000 claims description 102
- 229910021536 Zeolite Inorganic materials 0.000 claims description 95
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 91
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 70
- 239000004005 microsphere Substances 0.000 claims description 63
- 229910001679 gibbsite Inorganic materials 0.000 claims description 59
- 239000000203 mixture Substances 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 41
- 229910001593 boehmite Inorganic materials 0.000 claims description 40
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 23
- 229910001868 water Inorganic materials 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 14
- 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 claims description 12
- 229910001680 bayerite Inorganic materials 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 150000002910 rare earth metals Chemical class 0.000 claims description 10
- -1 sodium cations Chemical class 0.000 claims description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 3
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 claims description 2
- 229910052676 chabazite Inorganic materials 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 description 18
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 13
- 239000005995 Aluminium silicate Substances 0.000 description 12
- 235000012211 aluminium silicate Nutrition 0.000 description 12
- 229910052727 yttrium Inorganic materials 0.000 description 12
- 239000004927 clay Substances 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 6
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052863 mullite Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
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- 239000002245 particle Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000004523 catalytic cracking Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- 229910052769 Ytterbium Inorganic materials 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical group [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical class N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011162 ammonium carbonates Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
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Classifications
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- 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
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
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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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- 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
- B01J23/18—Arsenic, antimony or bismuth
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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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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/001—Calcining
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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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
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- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
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- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Description
本出願は、2017年4月14日に出願された米国仮出願第62/485,682号の優先権の利益を主張するものであり、その内容は、その全体が本明細書に組み込まれる。
一態様では、微小球流動接触分解(FCC)触媒が提供される。触媒は、ゼオライトと、70μmol/g未満の強いルイス部位密度を含むアルミナと、を含む。いくつかの実施形態では、アルミナは、フラッシュ焼成されたギブサイトに由来する。いくつかの実施形態では、FCC触媒は、フラッシュ焼成されたギブサイトに由来する約10重量%~約60重量%のアルミナを含む。いくつかの実施形態では、フラッシュ焼成されたギブサイトは、水和型のフラッシュ焼成されたギブサイトである。
非ゼオライト系材料、および70μmol/g未満の強いルイス部位密度を有するアルミナを含む前駆体微小球を予備形成することと、
前駆体微小球上のゼオライトをインサイチュ結晶化させて、ゼオライト系微小球材料を提供することと、を含む。
前駆体微小球をケイ酸ナトリウム、水酸化ナトリウム、および水と混合して、アルカリ性スラリーを得ることと、
アルカリ性スラリーを、微小球中の少なくとも約15重量%のYゼオライトを結晶化させるのに十分な温度まで、かつ十分な時間、加熱することと、を含む。
理論に束縛されるものではないが、約70μmol/g未満の強いルイス部位密度を含むアルミナを含有するFCC触媒は、ボトム選択性の改善を実証し得ると考えられる。希土類またはアルカリ土類をドープしたアルミナは、より大きな改善を実証するはずである。「ボトム」とは、重質サイクル油(HCO)としても知られる分解軽油の最も重い画分を指し、ほとんど価値がない。LCO(軽質サイクル油)は、さらに精製されるとLCOがディーゼル燃料に変換されるため、はるかに価値がある。したがって、変換の関数としてLCO/ボトム比を最大化する触媒(FCCの変換は、典型的には、100-LCO-ボトムとして定義される)が望ましい。
参照資料
1.Kayser,John C.,U.S.Patent No.6,069.012.
2.Frederic Thibault-Starzyk,Barbara Gil,Sebastien Aiello,Therese Chevreau,Jean-Pierre Gilson,“In situ thermogravimetry in an infrared spectrometer:an answer to quantitative spectroscopy of adsorbed species on heterogeneous catalysts,”Microporous and Mesoporous Materials,vol.67,107-112,2004.
3.Gary G.Christoph,Charles E.Corbato,Douglas A.Hofmann,Rodney T.Tettenhorse,“The Crystal Structure of Boehmite,Clay and Clay Minerals,vol.27,81-86,1979.
4.K.I.Shefer,S.V.Cherepanova,E.M.Moroz,E.Yu Gerasimov,S.V.Tsybulya,“Features of the real structure of pseudoboehmites:violations of the structure and layer packing caused by crystallization water”,Journal of Structural Chemistry,vol.51,132-141,2010.
Claims (14)
- ゼオライトと、約70μmol/g未満の強いルイス部位密度を含むアルミナと、を含む、微小球流動接触分解(FCC)触媒であって、
少なくとも35重量%のゼオライトを含む相組成を有する、前記触媒。 - 前記強いルイス部位密度が、約40μmol/g未満である、請求項1に記載の触媒。
- フラッシュ焼成されたギブサイトに由来する前記アルミナを約10重量%~約60重量%含む、請求項1に記載の触媒。
- 前記フラッシュ焼成されたギブサイトが、水和型のフラッシュ焼成されたギブサイトである、請求項3に記載の触媒。
- 前記アルミナが、ベーマイト、バイヤライト、またはそれらの混合物から形成され、前記ベーマイト、バイヤライト、またはそれらの混合物が、ランタン、ストロンチウム、またはビスマスの塩でドープされた水和型のフラッシュ焼成されたギブサイトに由来する、請求項1に記載の触媒。
- 前記アルミナが、希土類元素、ビスマス、アルカリ土類元素、またはそれらの任意の2つ以上の混合物をさらに含む、請求項1に記載の触媒。
- 前記アルミナが、約0.1重量%~約12重量%の量で前記希土類元素またはアルカリ土類元素を含む、請求項6に記載の触媒。
- 前記ゼオライトが、ゼオライトX、Yゼオライト、ZSM-5、ベータゼオライト、ZSM-11、ZSM-14、ZSM-17、ZSM-18、ZSM-20、ZSM-31、ZSM-34、ZSM-41、ZSM-46、モルデナイト、チャバザイト、およびそれらの2つ以上の混合物からなる群から選択され、前記触媒が、少なくとも60重量%のゼオライトを含む相組成を有する、請求項1に記載の触媒。
- 前記相組成が、少なくとも約30重量%のアモルファス材料をさらに含む、請求項8に記載の触媒。
- 前記ゼオライトが、Y-ゼオライトであり、かつイオン交換されて、前記触媒のナトリウム含有量を0.7重量%未満のNa2Oに低減させる、請求項1~9のいずれか一項に記載の触媒。
- ゼオライト系流動接触分解触媒の作製方法であって、前記方法が、
非ゼオライト系材料と、フラッシュ焼成されたギブサイトに由来し、70μmol/g未満の強いルイス部位密度とを含むアルミナ、を含む前駆体微小球を予備形成することと、
ゼオライト系微小球材料を提供するために、前記予備形成された微小球上のゼオライトをインサイチュ結晶化させることと、を含み、
前記インサイチュ結晶化が、
アルカリ性スラリーを得るために前記前駆体微小球をケイ酸ナトリウム、水酸化ナトリウム、および水と混合することと;
前記アルカリ性スラリーを、微小球中の少なくとも約15重量%のNaYゼオライトを結晶化させるのに十分な温度まで、かつ十分な時間、加熱することと;を含み、
少なくとも40重量%のYゼオライトが、予備形成された微小球の中または上で結晶化される、前記方法。 - 前記ゼオライト系微小球材料をアルカリ性スラリーの少なくとも大部分から分離することと、
前記ゼオライト系微小球材料中のナトリウムカチオンをアンモニウムイオンと交換させ、その後希土類イオンと交換させることと、をさらに含む、請求項11に記載の方法。 - 前記ゼオライト系微小球材料の焼成することと、
前記Na2Oの含有量が0.2%未満まで低減するように、前記ゼオライト系微小球材料をアンモニウムイオンとさらに交換させることと、
前記ゼオライト系微小球材料をさらに焼成することと、をさらに含む、請求項11または12に記載の方法。 - 各焼成が独立して、約500℃~約750℃の温度で少なくとも約2時間行われる、請求項13に記載の方法。
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