CA2468152C - Nox reduction composition for use in fcc processes - Google Patents
Nox reduction composition for use in fcc processes Download PDFInfo
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- CA2468152C CA2468152C CA2468152A CA2468152A CA2468152C CA 2468152 C CA2468152 C CA 2468152C CA 2468152 A CA2468152 A CA 2468152A CA 2468152 A CA2468152 A CA 2468152A CA 2468152 C CA2468152 C CA 2468152C
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- Prior art keywords
- oxide
- composition
- catalyst
- cracking catalyst
- alumina
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- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 43
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 34
- 230000002378 acidificating effect Effects 0.000 claims abstract description 29
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 12
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- -1 praseodymium oxide Chemical compound 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000004332 silver Substances 0.000 claims abstract 2
- 239000003054 catalyst Substances 0.000 claims description 70
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 48
- 239000002245 particle Substances 0.000 claims description 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 43
- 238000005336 cracking Methods 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- 229910052723 transition metal Inorganic materials 0.000 claims description 12
- 150000003624 transition metals Chemical class 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 230000008929 regeneration Effects 0.000 claims description 10
- 238000011069 regeneration method Methods 0.000 claims description 10
- 239000005995 Aluminium silicate Substances 0.000 claims description 9
- 235000012211 aluminium silicate Nutrition 0.000 claims description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000003518 caustics Substances 0.000 claims description 8
- 239000004005 microsphere Substances 0.000 claims description 8
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 7
- 150000002602 lanthanoids Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000002386 leaching Methods 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims 1
- 229910000311 lanthanide oxide Inorganic materials 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000000654 additive Substances 0.000 description 24
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 20
- 230000000996 additive effect Effects 0.000 description 17
- 239000000571 coke Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 238000004523 catalytic cracking Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 229910052815 sulfur oxide Inorganic materials 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910002637 Pr6O11 Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 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 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000001473 noxious effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- JCCNYMKQOSZNPW-UHFFFAOYSA-N loratadine Chemical compound C1CN(C(=O)OCC)CCC1=C1C2=NC=CC=C2CCC2=CC(Cl)=CC=C21 JCCNYMKQOSZNPW-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Chemical group 0.000 description 1
- 239000011733 molybdenum Chemical group 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Chemical group 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- B01J35/19—
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
- B01J38/30—Treating with free oxygen-containing gas in gaseous suspension, e.g. fluidised bed
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/515—Specific contaminant removal
Abstract
A composition for controlling Nox emission during FCC processes comprises (i) an acidic oxide support, (ii) cerium oxide, (iii) a lanthanide oxide other than ceria such as praseodymium oxide, and (iv), optionally, an oxide of a metal from Groups Ib and IIb such as copper, silver and zinc.
Description
NO, REDUCTION COMPOSITION
FOR USE IN FCC PROCESSES
BACKGROUND OF THE INVENTION
A major industrial problem involves the development of efficient methods for reducing the concentration of air pollutants, such as carbon monoxide, sulfur oxides and nitrogen oxides in waste gas streams which result from the processing and combustion of sulfur, carbon and nitrogen containing fuels. The discharge of these waste gas streams into the atmosphere is environmentally undesirable at the sulfur oxide, carbon monoxide and nitrogen oxide concentrations that are frequently encountered in conventional operations. The regeneration of cracking catalyst, which has been deactivated by coke deposits in the catalytic cracking of sulfur and nitrogen containing hydrocarbon feedstocks, is a typical example of a process which can result in a waste gas stream containing relatively high levels of carbon monoxide, sulfur and nitrogen oxides.
Catalytic cracking of heavy petroleum fractions is one of the major refining operations employed in the conversion of crude petroleum oils to useful products such as the fuels utilized by internal combustion engines.
In fluidized catalytic cracking processes, high molecular weight hydrocarbon liquids and vapors are contacted with hot, finely-divided, solid catalyst particles, either in a fluidized bed reactor or in an elongated transfer line reactor, and maintained at an elevated temperature in a fluidized or dispersed state for a period of time sufficient to effect the desired degree of cracking to lower molecular weight hydrocarbons of the kind typically present in motor gasoline and distillate fuels.
In the catalytic cracking of hydrocarbons, some nonvolatile carbonaceous material or coke is deposited on the catalyst particles. Coke comprises highly condensed aromatic hydrocarbons and generally contains from about 4 to about 10 weight percent hydrogen. When the hydrocarbon feedstock contains organic sulfur and nitrogen compounds, the coke also contains sulfur and nitrogen. As coke accumulates on the cracking catalyst, the activity of the catalyst for cracking and the selectivity of the catalyst for producing gasoline blending stocks diminishes.
Catalyst which has become substantially deactivated through the deposit of coke is continuously withdrawn from the reaction zone. This deactivated catalyst is conveyed to a stripping zone where volatile deposits are removed with an inert gas at elevated temperatures. The catalyst particles are then reactivated to essentially their original capabilities by substantial removal of the coke deposits in a suitable regeneration process.
Regenerated catalyst is then continuously returned to the reaction zone to repeat the 'cycle.
Catalyst regeneration is accomplished by burning the coke deposits from the catalyst surfaces with an oxygen containing gas such as air. The combustion of these coke deposits can be regarded, in a simplified manner, as the oxidation of carbon and the products are carbon monoxide and carbon dioxide.
When sulfur and nitrogen containing feedstocks are utilized in catalytic cracking process, the coke deposited on the catalyst contains sulfur and nitrogen. During regeneration of coked deactivated catalyst, the coke is burned from the catalyst surface that then results in the conversion 20. of sulfur to sulfur oxides and nitrogen to nitrogen oxides.
The conditions experienced by the catalyst in a fluid catalytic cracking (FCC) unit are very severe. Catalyst is continuously being cycled between reductive atmosphere on the reactor side to an oxidative atmosphere on the regenerator side. The temperatures between the two zones are different so the catalyst experiences thermal shocks. Also the regenerator contains nominally about 15-25% steam. All these factors lead to a significant decline in the catalyst activity and fresh catalyst needs to be continuously added to maintain the cracking activity.
Various approaches have been used to either reduce the formation of noxious gases or treat them after they are formed. Most typically, additives have been used either as an integral part of the FCC catalyst particles or as separate particles in admixture with the FCC catalyst.
FOR USE IN FCC PROCESSES
BACKGROUND OF THE INVENTION
A major industrial problem involves the development of efficient methods for reducing the concentration of air pollutants, such as carbon monoxide, sulfur oxides and nitrogen oxides in waste gas streams which result from the processing and combustion of sulfur, carbon and nitrogen containing fuels. The discharge of these waste gas streams into the atmosphere is environmentally undesirable at the sulfur oxide, carbon monoxide and nitrogen oxide concentrations that are frequently encountered in conventional operations. The regeneration of cracking catalyst, which has been deactivated by coke deposits in the catalytic cracking of sulfur and nitrogen containing hydrocarbon feedstocks, is a typical example of a process which can result in a waste gas stream containing relatively high levels of carbon monoxide, sulfur and nitrogen oxides.
Catalytic cracking of heavy petroleum fractions is one of the major refining operations employed in the conversion of crude petroleum oils to useful products such as the fuels utilized by internal combustion engines.
In fluidized catalytic cracking processes, high molecular weight hydrocarbon liquids and vapors are contacted with hot, finely-divided, solid catalyst particles, either in a fluidized bed reactor or in an elongated transfer line reactor, and maintained at an elevated temperature in a fluidized or dispersed state for a period of time sufficient to effect the desired degree of cracking to lower molecular weight hydrocarbons of the kind typically present in motor gasoline and distillate fuels.
In the catalytic cracking of hydrocarbons, some nonvolatile carbonaceous material or coke is deposited on the catalyst particles. Coke comprises highly condensed aromatic hydrocarbons and generally contains from about 4 to about 10 weight percent hydrogen. When the hydrocarbon feedstock contains organic sulfur and nitrogen compounds, the coke also contains sulfur and nitrogen. As coke accumulates on the cracking catalyst, the activity of the catalyst for cracking and the selectivity of the catalyst for producing gasoline blending stocks diminishes.
Catalyst which has become substantially deactivated through the deposit of coke is continuously withdrawn from the reaction zone. This deactivated catalyst is conveyed to a stripping zone where volatile deposits are removed with an inert gas at elevated temperatures. The catalyst particles are then reactivated to essentially their original capabilities by substantial removal of the coke deposits in a suitable regeneration process.
Regenerated catalyst is then continuously returned to the reaction zone to repeat the 'cycle.
Catalyst regeneration is accomplished by burning the coke deposits from the catalyst surfaces with an oxygen containing gas such as air. The combustion of these coke deposits can be regarded, in a simplified manner, as the oxidation of carbon and the products are carbon monoxide and carbon dioxide.
When sulfur and nitrogen containing feedstocks are utilized in catalytic cracking process, the coke deposited on the catalyst contains sulfur and nitrogen. During regeneration of coked deactivated catalyst, the coke is burned from the catalyst surface that then results in the conversion 20. of sulfur to sulfur oxides and nitrogen to nitrogen oxides.
The conditions experienced by the catalyst in a fluid catalytic cracking (FCC) unit are very severe. Catalyst is continuously being cycled between reductive atmosphere on the reactor side to an oxidative atmosphere on the regenerator side. The temperatures between the two zones are different so the catalyst experiences thermal shocks. Also the regenerator contains nominally about 15-25% steam. All these factors lead to a significant decline in the catalyst activity and fresh catalyst needs to be continuously added to maintain the cracking activity.
Various approaches have been used to either reduce the formation of noxious gases or treat them after they are formed. Most typically, additives have been used either as an integral part of the FCC catalyst particles or as separate particles in admixture with the FCC catalyst.
The additive that has gained the widest acceptance for lowering sulfur oxide emissions to date in FCC units (FCCU) is based upon Magnesium oxide/Magnesium aluminate/ceria technology. Pt supported on clay or alumina is most commonly used as an additive for lowering of carbon monoxide emissions. Unfortunately the additives used to control CO emissions typically cause a dramatic increase (e.g. >300%) in NOX
evolution from the regenerator.
Various approaches have been used to treat nitric oxide gases in FCCU. For example, US 5,037,538 describes the reduction of oxides of nitrogen (NOx) emissions from an FCC regenerator by adding a deNOx catalyst to the FCC regenerator in a form whereby the deNOx catalyst remains segregated within the FCC regenerator.
US 5,085,762 describes the reduction of emissions of noxious nitrogen oxides with the flue gas from the regenerator of a fluid catalytic cracking plant by incorporating into the circulating inventory of cracking catalyst separate additive particles that contain a copper-loaded zeolite material having a characteristic structure with a defined X-ray diffraction pattern.
US 5,002,654 describes a process for regeneration of cracking catalyst while minimizing NOx emissions using a zinc-based deNOx catalyst.
US 5,021,146 describes a process for regeneration of cracking catalyst while minimizing NOx emissions using a Group Illb based deNOx additive.
US 5,364,517 and US 5,364,517 describe the reduction of the NOx content of FCC regenerator flue gas is reduced using a spinel/perovskite additive.
US 5,750,020 and US 5,591,418 describe process for removing sulfur oxides or nitrogen oxides from a gaseous mixture in an FCC
process using a collapsed composition which is substantially composed of microcrystallites collectively of the formula:
2+ 3+
M2m AI2-pMp TrL7+rs where M2+ is a divalent metal, M3+ is a trivalent metal, and T is vanadium, tungsten, or molybdenum.
US 6,165,933 describes compositions comprising a component containing (i) an acidic oxide support, (ii) an alkali metal and/or alkaline earth metal or mixtures thereof, (iii) a transition metal oxide having oxygen storage capability, and (iv) palladium; to promote CO combustion in FCC
processes while minimizing the formation of NOx.
US 6,129,834 and US 6,143,167 describe compositions comprising a component containing (i) an acidic oxide support, (ii) an alkali metal and/or alkaline earth metal or mixtures thereof, (iii) a transition metal oxide having oxygen storage capability, and (iv) a transition metal selected from Groups lb and/or Ilb of the Periodic Table; to provide NOx control performance in FCC processes.
All the additives added to FCC units need to have sufficient hydrothermal stability to withstand the severe environment of an FCCU
and there remains the need for NOx additives to be used in FCC that have improved hydrothermal stability.
SUMMARY OF THE INVENTION
The invention provides novel compositions suitable for use in FCC
processes that are capable of providing improved NO), control performance.
In one aspect, the invention provides compositions for reducing NO, emissions in FCC processes, the compositions containing (i) an acidic oxide support, (ii) ceria (iii) at least one oxide of a lanthanide series element other than ceria, and (iv), optionally, at least one oxide of a transition metal selected from Groups lb and Ilb of the Periodic Table. The acidic oxide support preferably contains alumina. Praseodymium oxide is the preferred lanthanide oxide other than ceria. Cu and Ag are preferred Group lb transition metals and Zn is the preferred Group Ilb transition metal.
In another aspect, the invention encompasses FCC processes 5 using the NOx reduction compositions of this invention either as an integral part of the FCC catalyst particles or as separate particles admixed with the FCC catalyst.
These and other aspects of the invention are described in further detail below.
DETAILED DESCRIPTION OF THE INVENTION
The invention encompasses the discovery that certain classes of compositions are very effective for the reduction of NO, gas emissions in FCC processes. Moreover, such compositions have unexpectedly improved hydrothermal stability over prior art compositions. The NOX
reduction compositions of the inventions are characterized in that they comprise (i) an acidic oxide support, (ii) cerium oxide (iii) at least one oxide of a lanthanide series element other than ceria, and (iv), optionally, at least one oxide of a transition metal selected from Groups lb and Ilb of the Periodic Table and mixtures thereof.
The acidic oxide support should be of sufficient acidity for the composition to act as an effective NOX reduction additive. Acidic oxide catalyst supports are well know to those of ordinary skill in the art and include, for example, transitional aluminas such as gamma and eta alumina, silica-stabilized versions of said aluminas, including the silica-stabilized alumina spinel formed by leaching silica from kaolin calcined through its characteristic exotherm to form the spinel, or mullite. The support may be crystalline or amorphous. Preferably, the acidic oxide support contains at least some alumina. More preferably, the oxide support contains at least 50 wt. % alumina. The oxide support is preferably an oxide selected from the group consisting of alumina and silica-alumina. Where an amorphous silica-alumina support is used, the support preferably has an alumina to silica molar ratio of from about 1: 1 up to about 50: 1. Examples of commercially available acidic oxide alumina supports are available under tradenames such as PURALOX, CATAPAL and VERSAL. Examples of commercially available acidic silica-alumina supports are available under the tradenames such as SIRAL and SIRALOX.
The silica-alumina support can optionally be created by the caustic leaching of silica from preformed kaolin microspheres as described in US
Patents 4,847, 225 and 4,628, 042. Preferably, the kaolin that is subject to caustic leaching is calcined substantially through its characteristic exotherm to form spinel and/or mullite. More preferably, the caustic leached kaolin support is a microsphere whereby the caustic leached kaolin is bound with aluminum chlorohydroxide before calcination through the exotherm.
The acidic oxide support further preferably has sufficient surface area to facilitate the NOx reduction process. Preferably, the oxide support has a surface area of at least about 20 m2/g, more preferably from about 50 up to about 300 m2/g. The acidic oxide support may be a powder which is preferable when used as an integral part of the FCC catalyst or a microsphere or particle, preferably when used as an admixture with FCC catalysts.
The amount of the cerium oxide (ceria) present in the NOx reduction composition may be varied considerably relative to the amount of acidic oxide support. Preferably, the NOx reduction composition contains at least about 0.5 part by weight of cerium oxide per 100 parts by weight of the acidic oxide support material, more preferably from at least about 1 part by weight up to about 25 parts by weight of cerium oxide per 100 parts of the acidic oxide support material.
The lanthanide oxides other than ceria include at least one metal oxide having oxygen storage capability similar to that of ceria. Preferably, the lanthanide oxide other than ceria is praseodymium oxide. The amount of the lanthanide oxide other than ceria present in the NOx reduction composition may be varied considerably relative to the amount of acidic oxide support. Preferably, the NOx reduction composition contains from at least about 0.05 part by weight of oxide per 100 parts by weight of the acidic oxide support material, more preferably from at least about 1 part by weight up to about 25 parts by weight of lanthanide oxide other than ceria mixture per 100 parts of the acidic oxide support material. The amount of ceria to the lanthanide oxides other than ceria present in the NOx reduction composition of this invention ranges, from 1:4 to 4:1 by weight, preferably 1:2 to 2:1.
The Group lb and/or Ilb transition metals may be any metal or combination of metals selected from those groups of the Periodic Table.
Preferably, the transition metal is selected from the group consisting of Cu, Ag, Zn and mixtures thereof. The amount of transition metal present is preferably at least about 100 parts by weight (measured as metal oxide) per million parts of the oxide support material, more preferably from about 0.1 up to about 5 parts by weight per 100 parts of the oxide support material.
The NO), reduction composition may contain minor amounts of other materials, which preferably do not adversely affect the NOx reduction function in a significant way. The NOx reduction composition may consist essentially of items (i)-(iv) mentioned above. Where the composition of the invention is used as an additive particle for an FCC process, the NOx reduction composition may be combined with fillers (e.g. clay, silica-alumina, silica and/or alumina particles) and/or binders (e.g. silica sol, alumina sol, silica alumina sol, etc.) to form particles suitable for use in an FCC process, preferably by spray drying before the calcination of step.
More preferably, porous particles, also known as microspheres, are formed from acidic oxide support typically by spray drying powdered oxide support material combined with a binder/filler before or after impregnation with the individual constituents. Preferably, any added binders or fillers used do not significantly adversely affect the performance of the NOx reduction component.
evolution from the regenerator.
Various approaches have been used to treat nitric oxide gases in FCCU. For example, US 5,037,538 describes the reduction of oxides of nitrogen (NOx) emissions from an FCC regenerator by adding a deNOx catalyst to the FCC regenerator in a form whereby the deNOx catalyst remains segregated within the FCC regenerator.
US 5,085,762 describes the reduction of emissions of noxious nitrogen oxides with the flue gas from the regenerator of a fluid catalytic cracking plant by incorporating into the circulating inventory of cracking catalyst separate additive particles that contain a copper-loaded zeolite material having a characteristic structure with a defined X-ray diffraction pattern.
US 5,002,654 describes a process for regeneration of cracking catalyst while minimizing NOx emissions using a zinc-based deNOx catalyst.
US 5,021,146 describes a process for regeneration of cracking catalyst while minimizing NOx emissions using a Group Illb based deNOx additive.
US 5,364,517 and US 5,364,517 describe the reduction of the NOx content of FCC regenerator flue gas is reduced using a spinel/perovskite additive.
US 5,750,020 and US 5,591,418 describe process for removing sulfur oxides or nitrogen oxides from a gaseous mixture in an FCC
process using a collapsed composition which is substantially composed of microcrystallites collectively of the formula:
2+ 3+
M2m AI2-pMp TrL7+rs where M2+ is a divalent metal, M3+ is a trivalent metal, and T is vanadium, tungsten, or molybdenum.
US 6,165,933 describes compositions comprising a component containing (i) an acidic oxide support, (ii) an alkali metal and/or alkaline earth metal or mixtures thereof, (iii) a transition metal oxide having oxygen storage capability, and (iv) palladium; to promote CO combustion in FCC
processes while minimizing the formation of NOx.
US 6,129,834 and US 6,143,167 describe compositions comprising a component containing (i) an acidic oxide support, (ii) an alkali metal and/or alkaline earth metal or mixtures thereof, (iii) a transition metal oxide having oxygen storage capability, and (iv) a transition metal selected from Groups lb and/or Ilb of the Periodic Table; to provide NOx control performance in FCC processes.
All the additives added to FCC units need to have sufficient hydrothermal stability to withstand the severe environment of an FCCU
and there remains the need for NOx additives to be used in FCC that have improved hydrothermal stability.
SUMMARY OF THE INVENTION
The invention provides novel compositions suitable for use in FCC
processes that are capable of providing improved NO), control performance.
In one aspect, the invention provides compositions for reducing NO, emissions in FCC processes, the compositions containing (i) an acidic oxide support, (ii) ceria (iii) at least one oxide of a lanthanide series element other than ceria, and (iv), optionally, at least one oxide of a transition metal selected from Groups lb and Ilb of the Periodic Table. The acidic oxide support preferably contains alumina. Praseodymium oxide is the preferred lanthanide oxide other than ceria. Cu and Ag are preferred Group lb transition metals and Zn is the preferred Group Ilb transition metal.
In another aspect, the invention encompasses FCC processes 5 using the NOx reduction compositions of this invention either as an integral part of the FCC catalyst particles or as separate particles admixed with the FCC catalyst.
These and other aspects of the invention are described in further detail below.
DETAILED DESCRIPTION OF THE INVENTION
The invention encompasses the discovery that certain classes of compositions are very effective for the reduction of NO, gas emissions in FCC processes. Moreover, such compositions have unexpectedly improved hydrothermal stability over prior art compositions. The NOX
reduction compositions of the inventions are characterized in that they comprise (i) an acidic oxide support, (ii) cerium oxide (iii) at least one oxide of a lanthanide series element other than ceria, and (iv), optionally, at least one oxide of a transition metal selected from Groups lb and Ilb of the Periodic Table and mixtures thereof.
The acidic oxide support should be of sufficient acidity for the composition to act as an effective NOX reduction additive. Acidic oxide catalyst supports are well know to those of ordinary skill in the art and include, for example, transitional aluminas such as gamma and eta alumina, silica-stabilized versions of said aluminas, including the silica-stabilized alumina spinel formed by leaching silica from kaolin calcined through its characteristic exotherm to form the spinel, or mullite. The support may be crystalline or amorphous. Preferably, the acidic oxide support contains at least some alumina. More preferably, the oxide support contains at least 50 wt. % alumina. The oxide support is preferably an oxide selected from the group consisting of alumina and silica-alumina. Where an amorphous silica-alumina support is used, the support preferably has an alumina to silica molar ratio of from about 1: 1 up to about 50: 1. Examples of commercially available acidic oxide alumina supports are available under tradenames such as PURALOX, CATAPAL and VERSAL. Examples of commercially available acidic silica-alumina supports are available under the tradenames such as SIRAL and SIRALOX.
The silica-alumina support can optionally be created by the caustic leaching of silica from preformed kaolin microspheres as described in US
Patents 4,847, 225 and 4,628, 042. Preferably, the kaolin that is subject to caustic leaching is calcined substantially through its characteristic exotherm to form spinel and/or mullite. More preferably, the caustic leached kaolin support is a microsphere whereby the caustic leached kaolin is bound with aluminum chlorohydroxide before calcination through the exotherm.
The acidic oxide support further preferably has sufficient surface area to facilitate the NOx reduction process. Preferably, the oxide support has a surface area of at least about 20 m2/g, more preferably from about 50 up to about 300 m2/g. The acidic oxide support may be a powder which is preferable when used as an integral part of the FCC catalyst or a microsphere or particle, preferably when used as an admixture with FCC catalysts.
The amount of the cerium oxide (ceria) present in the NOx reduction composition may be varied considerably relative to the amount of acidic oxide support. Preferably, the NOx reduction composition contains at least about 0.5 part by weight of cerium oxide per 100 parts by weight of the acidic oxide support material, more preferably from at least about 1 part by weight up to about 25 parts by weight of cerium oxide per 100 parts of the acidic oxide support material.
The lanthanide oxides other than ceria include at least one metal oxide having oxygen storage capability similar to that of ceria. Preferably, the lanthanide oxide other than ceria is praseodymium oxide. The amount of the lanthanide oxide other than ceria present in the NOx reduction composition may be varied considerably relative to the amount of acidic oxide support. Preferably, the NOx reduction composition contains from at least about 0.05 part by weight of oxide per 100 parts by weight of the acidic oxide support material, more preferably from at least about 1 part by weight up to about 25 parts by weight of lanthanide oxide other than ceria mixture per 100 parts of the acidic oxide support material. The amount of ceria to the lanthanide oxides other than ceria present in the NOx reduction composition of this invention ranges, from 1:4 to 4:1 by weight, preferably 1:2 to 2:1.
The Group lb and/or Ilb transition metals may be any metal or combination of metals selected from those groups of the Periodic Table.
Preferably, the transition metal is selected from the group consisting of Cu, Ag, Zn and mixtures thereof. The amount of transition metal present is preferably at least about 100 parts by weight (measured as metal oxide) per million parts of the oxide support material, more preferably from about 0.1 up to about 5 parts by weight per 100 parts of the oxide support material.
The NO), reduction composition may contain minor amounts of other materials, which preferably do not adversely affect the NOx reduction function in a significant way. The NOx reduction composition may consist essentially of items (i)-(iv) mentioned above. Where the composition of the invention is used as an additive particle for an FCC process, the NOx reduction composition may be combined with fillers (e.g. clay, silica-alumina, silica and/or alumina particles) and/or binders (e.g. silica sol, alumina sol, silica alumina sol, etc.) to form particles suitable for use in an FCC process, preferably by spray drying before the calcination of step.
More preferably, porous particles, also known as microspheres, are formed from acidic oxide support typically by spray drying powdered oxide support material combined with a binder/filler before or after impregnation with the individual constituents. Preferably, any added binders or fillers used do not significantly adversely affect the performance of the NOx reduction component.
Where the NO, reduction composition is used as an additive particulate (as opposed to being integrated into the FCC catalyst particles themselves), the amount of NO, reduction component in the additive particles is preferably at least 50 wt %, more preferably at least 75 wt. %.
Most preferably, the additive particles consist entirely of the NO), reduction component. The additive particles are preferably of a size suitable for circulation with the catalyst inventory in an FCC process. The additive particles preferably have an average particle size of about 20-200 pm.
The additive particles preferably have attrition characteristics such that they can withstand the severe environment of an FCCU.
As previously mentioned the NO), reduction composition of the invention may be integrated into the FCC catalyst particles themselves. In such case, any conventional FCC catalyst particle components may be used in combination with the NO), reduction composition of the invention.
If integrated into the FCC catalyst particles the NO, reduction composition of the invention preferably represents at least about 0.02 wt. % the FCC
catalyst particle, more preferably about 0.1-10 wt. %.
While the invention is not limited to any particular method of manufacture, the NO, reduction composition of the invention is preferably made by the following procedures:
(a) co-impregnate the acidic oxide support particles with a cerium oxide source, at least one lanthanide oxide source other than ceria, and, optionally, at least one source of a Group 1 b/Ilb element.
25. (b) calcine the impregnated support of step (a).
The sources of oxides are preferably slurries, sols and/or solutions of the metal oxides themselves or salts of the respective metals, which decompose to oxides on calcination, or combinations of oxides and salts.
If desired, the individual constituents may be separately added to the support particles with a calcination step in between each addition. The calcination steps are preferably performed at about 450-750 C.
The NOx reduction composition may be used as a separate additive particle or as an integral part of an FCC catalyst particle. If used as an additive, the NOx reduction component may itself be formed into particles suitable for use in a FCC process. Alternatively, the NOx reduction component may be combined with binders, fillers, etc. by any conventional technique. See for example, the process described in U. S. Pat. No.
5,194,413.
Where the NOx reduction component of the invention is integrated into an FCC catalyst particle, preferably the component is first formed and then combined with the other constituents which make up the FCC catalyst particle. Incorporation of the NOx reduction composition directly into FCC
catalyst particles may be accomplished by any known technique. Examples of suitable techniques for this purpose are disclosed in U. S. Pat. Nos.
3,957,689; 4,499,197; 4,542,188 and 4,458,623.
The compositions of the invention may be used in any conventional FCC process. Typical FCC processes are conducted at reaction temperatures of 450 to 650 C. with catalyst regeneration temperatures of 600 to 850 C. The compositions of the invention may be used in FCC processing of any typical hydrocarbon feedstocks. Preferably, the compositions of the invention are used in FCC processes involving the cracking of hydrocarbon feedstocks which contain above average amounts of nitrogen, especially residual feedstocks or feedstocks having a nitrogen content of at least 0.1 wt. %. The amount of the NOx reduction component of the invention used may vary depending on the specific FCC process. Preferably, the amount of NOx reduction component used (in the circulating inventory) is about 0.1-15 wt. %
based on the weight of the FCC catalyst in the circulating catalyst inventory.
The presence of the compositions of the invention during the FCC process catalyst regeneration step dramatically reduces the level of NOx emitted during regeneration while having improved hydrothermal stability.
Example 1 2% Pr6Oõ/10% Ce02/2% CuO/ Alumina Alumina support particles are coimpregnated with a solution of cerium and 5 praseodymium nitrate by incipient wetness, dried and calcined at 1200 F
for 2 hours to achieve a 10% CeO2 and 2 wt% Pr6011 level. On the microsphere,-copper nitrate is impregnated, dried and calcined at 1200 F
for 2 hours to achieve a 2 wt% CuO level.
Most preferably, the additive particles consist entirely of the NO), reduction component. The additive particles are preferably of a size suitable for circulation with the catalyst inventory in an FCC process. The additive particles preferably have an average particle size of about 20-200 pm.
The additive particles preferably have attrition characteristics such that they can withstand the severe environment of an FCCU.
As previously mentioned the NO), reduction composition of the invention may be integrated into the FCC catalyst particles themselves. In such case, any conventional FCC catalyst particle components may be used in combination with the NO), reduction composition of the invention.
If integrated into the FCC catalyst particles the NO, reduction composition of the invention preferably represents at least about 0.02 wt. % the FCC
catalyst particle, more preferably about 0.1-10 wt. %.
While the invention is not limited to any particular method of manufacture, the NO, reduction composition of the invention is preferably made by the following procedures:
(a) co-impregnate the acidic oxide support particles with a cerium oxide source, at least one lanthanide oxide source other than ceria, and, optionally, at least one source of a Group 1 b/Ilb element.
25. (b) calcine the impregnated support of step (a).
The sources of oxides are preferably slurries, sols and/or solutions of the metal oxides themselves or salts of the respective metals, which decompose to oxides on calcination, or combinations of oxides and salts.
If desired, the individual constituents may be separately added to the support particles with a calcination step in between each addition. The calcination steps are preferably performed at about 450-750 C.
The NOx reduction composition may be used as a separate additive particle or as an integral part of an FCC catalyst particle. If used as an additive, the NOx reduction component may itself be formed into particles suitable for use in a FCC process. Alternatively, the NOx reduction component may be combined with binders, fillers, etc. by any conventional technique. See for example, the process described in U. S. Pat. No.
5,194,413.
Where the NOx reduction component of the invention is integrated into an FCC catalyst particle, preferably the component is first formed and then combined with the other constituents which make up the FCC catalyst particle. Incorporation of the NOx reduction composition directly into FCC
catalyst particles may be accomplished by any known technique. Examples of suitable techniques for this purpose are disclosed in U. S. Pat. Nos.
3,957,689; 4,499,197; 4,542,188 and 4,458,623.
The compositions of the invention may be used in any conventional FCC process. Typical FCC processes are conducted at reaction temperatures of 450 to 650 C. with catalyst regeneration temperatures of 600 to 850 C. The compositions of the invention may be used in FCC processing of any typical hydrocarbon feedstocks. Preferably, the compositions of the invention are used in FCC processes involving the cracking of hydrocarbon feedstocks which contain above average amounts of nitrogen, especially residual feedstocks or feedstocks having a nitrogen content of at least 0.1 wt. %. The amount of the NOx reduction component of the invention used may vary depending on the specific FCC process. Preferably, the amount of NOx reduction component used (in the circulating inventory) is about 0.1-15 wt. %
based on the weight of the FCC catalyst in the circulating catalyst inventory.
The presence of the compositions of the invention during the FCC process catalyst regeneration step dramatically reduces the level of NOx emitted during regeneration while having improved hydrothermal stability.
Example 1 2% Pr6Oõ/10% Ce02/2% CuO/ Alumina Alumina support particles are coimpregnated with a solution of cerium and 5 praseodymium nitrate by incipient wetness, dried and calcined at 1200 F
for 2 hours to achieve a 10% CeO2 and 2 wt% Pr6011 level. On the microsphere,-copper nitrate is impregnated, dried and calcined at 1200 F
for 2 hours to achieve a 2 wt% CuO level.
10 Example 2 3% La 03/10% CeO2/3% Nd203/2% CuO/ Alumina Alumina support particles are coimpregnated with a solution of lanthanum, cerium and neodymium nitrate by incipient wetness, dried and calcined at 1200 F for 2 hours to achieve a 10% CeO2 and 2 wt% Nd2O3 level. On the microsphere, copper nitrate is impregnated, dried and calcined at 12009 F for 2 hours to achieve a 2 wt% CuO level Example 3 2% Pr6Oõ/10% Ce02/2% CuO/Alumina Alumina support particles are coimpregnated with a solution of cerium, praseodymium and copper nitrate by incipient wetness, dried and calcined at 1200 F for 2 hours to achieve a 10% CeO2/2% Pr6O11/ 2% CuO level.
Example 4 2% Pr6O11/10% Ce02/1.5% Nd203/ 2% CuO on Alumina Alumina support particles are coimpregnated with a solution of cerium, praseodymium and neodymium nitrate by incipient wetness, dried and calcined at 1200 F for 2 hours to achieve a 10% CeO2/10 wt% Pr60111.5%
Nd203 level. On this microsphere, copper nitrate is impregnated, dried and calcined at 1200 F for 2 hours to achieve a 2 wt% CuO level.
Example 4 2% Pr6O11/10% Ce02/1.5% Nd203/ 2% CuO on Alumina Alumina support particles are coimpregnated with a solution of cerium, praseodymium and neodymium nitrate by incipient wetness, dried and calcined at 1200 F for 2 hours to achieve a 10% CeO2/10 wt% Pr60111.5%
Nd203 level. On this microsphere, copper nitrate is impregnated, dried and calcined at 1200 F for 2 hours to achieve a 2 wt% CuO level.
COMPARATIVE EXAMPLES
Example A
3% Na20/10% Ce02/2% CuO on Alumina Alumina support particle are impregnated with sodium nitrate by incipient wetness, dried and calcined at 1200 F for 2 hours to achieve 3.0 wt%
Na20. The Na-containing alumina particles are coimpregnated with a solution of cerium and copper nitrate and calcined at 1200 F for 2 hours to achieve a 10 wt CeO2, 2% CuO level.
Example B
5% MgO/10% Ce02/2% CuO Alumina Alumina support particles are impregnated with magnesium nitrate by incipient wetness, dried and calcined at 1200 F for 2 hours to achieve a 5.0% MgO level. The Mg-containing alumina particles are coimpregnated with a solution of cerium and copper nitrate and calcined at 1200 F for 2 hours to achieve a 10% Ce02, 2 wt% CuO level.
Example C
10% CeO2 on Alumina Alumina support particles are impregnated with cerium nitrate by incipient wetness, dried and calcined at 1200 F for 2 hours to achieve a 10% CeO2 level.
Example D
10% Pr6011 on Alumina Alumina support particles are impregnated with praseodymium nitrate by incipient wetness, dried and calcined at 1200 F for 2 hours to achieve a 10% Pr6011 level.
Example A
3% Na20/10% Ce02/2% CuO on Alumina Alumina support particle are impregnated with sodium nitrate by incipient wetness, dried and calcined at 1200 F for 2 hours to achieve 3.0 wt%
Na20. The Na-containing alumina particles are coimpregnated with a solution of cerium and copper nitrate and calcined at 1200 F for 2 hours to achieve a 10 wt CeO2, 2% CuO level.
Example B
5% MgO/10% Ce02/2% CuO Alumina Alumina support particles are impregnated with magnesium nitrate by incipient wetness, dried and calcined at 1200 F for 2 hours to achieve a 5.0% MgO level. The Mg-containing alumina particles are coimpregnated with a solution of cerium and copper nitrate and calcined at 1200 F for 2 hours to achieve a 10% Ce02, 2 wt% CuO level.
Example C
10% CeO2 on Alumina Alumina support particles are impregnated with cerium nitrate by incipient wetness, dried and calcined at 1200 F for 2 hours to achieve a 10% CeO2 level.
Example D
10% Pr6011 on Alumina Alumina support particles are impregnated with praseodymium nitrate by incipient wetness, dried and calcined at 1200 F for 2 hours to achieve a 10% Pr6011 level.
As previously stated hydrothermal stability is an important property of FCC
catalysts and additives. Different methods are known in the art to perform accelerated hydrothermal deactivation of FCC catalysts and additives in the laboratory. The most common procedure for hydrothermal laboratory deactivation is to steam the catalyst or additive in the presence of 100%
steam at temperatures ranging from 1300 to 1500 F for 4 to 8 hours. The additives tested were deactivated by steaming at 1500 F for 4 hours in 100% steam. NO uptakes were measured at room temperature on the additive after reduction in hydrogen at 1000 F. Data from NO uptake tests using Examples 1-4 and A-D are shown below in Table 1. NO uptake retention is the percentage of the NO uptake capacity retained after steaming.
Table 1 NO uptake x 10 NO uptake retention, %
Mol/g (As-is -Steamed) Example A 1.39 22 Example B 1.13 28 Example C 0.75 30 Example D 0.58 32 Example 1 4.45 65 Example 2 4.9 67 Example 3 4.61 67 Example 4 3.58 64 As can be seen, Examples 1 through 4, within the scope of the present invention, yielded substantial NO uptake and NO uptake retention relative to Examples A and D. The results of the testing are particularly unexpected in that each of ceria and praseodymium oxide alone yielded little NO uptake (Examples C and D).
catalysts and additives. Different methods are known in the art to perform accelerated hydrothermal deactivation of FCC catalysts and additives in the laboratory. The most common procedure for hydrothermal laboratory deactivation is to steam the catalyst or additive in the presence of 100%
steam at temperatures ranging from 1300 to 1500 F for 4 to 8 hours. The additives tested were deactivated by steaming at 1500 F for 4 hours in 100% steam. NO uptakes were measured at room temperature on the additive after reduction in hydrogen at 1000 F. Data from NO uptake tests using Examples 1-4 and A-D are shown below in Table 1. NO uptake retention is the percentage of the NO uptake capacity retained after steaming.
Table 1 NO uptake x 10 NO uptake retention, %
Mol/g (As-is -Steamed) Example A 1.39 22 Example B 1.13 28 Example C 0.75 30 Example D 0.58 32 Example 1 4.45 65 Example 2 4.9 67 Example 3 4.61 67 Example 4 3.58 64 As can be seen, Examples 1 through 4, within the scope of the present invention, yielded substantial NO uptake and NO uptake retention relative to Examples A and D. The results of the testing are particularly unexpected in that each of ceria and praseodymium oxide alone yielded little NO uptake (Examples C and D).
Claims (23)
1. A NOx removal composition suitable for reducing NOx emissions during catalyst regeneration in a fluid catalytic cracking process, said composition comprising (i) an acidic oxide support, (ii) cerium oxide, (iii) at least one oxide of a lanthanide series element other than cerium oxide, and (iv) at least one oxide of a transition metal selected from Groups Ib and IIb of the Periodic Table and mixtures thereof, wherein the ratio of (ii) to (iii) ranges from at least 1.66 : 1 by weight.
2. The composition of claim 1 wherein said acidic oxide support is selected from the group consisting of alumina and silica-alumina.
3. The composition of claim 2 wherein said acidic oxide support is alumina.
4. The composition of claim 2 wherein said acidic oxide support is silica-alumina.
5. The composition of claim 4 wherein said silica alumina has an alumina :
silica mole ratio of from 1: 1 up to 50: 1.
silica mole ratio of from 1: 1 up to 50: 1.
6. The composition of claim 4 wherein the said silica-alumina is prepared by caustic leaching of silica from calcined kaolin.
7. The composition of claim 4 wherein the said silica-alumina is prepared by the caustic leaching of silica from kaolin calcined through its characteristic exotherm.
8. The composition of claim 7 where the caustic leached kaolin support is a microsphere whereby the caustic leached kaolin is bound with aluminum chlorohydroxide before calcination through its characteristic exotherm.
9. The composition of claim 1 wherein said Group Ib and IIb transition metals are selected from the group consisting of copper, silver, zinc and mixtures thereof.
10. The composition of claim 1 wherein said cerium oxide is present in amounts of from at least 0.5 part by weight per 100 parts by weight of said acidic oxide support.
11. The composition of claim 1 wherein said oxide of a lanthanide series element other than cerium oxide is praseodymium oxide.
12. A fluid cracking catalyst composition comprising (a) a cracking component suitable for catalyzing the cracking of hydrocarbons, and (b) a NOx reduction composition comprising (i) an acidic oxide support, (ii) cerium oxide, (iii) at least one oxide of a lanthanide series element other than ceria, and (iv) an oxide of a transition metal selected from Groups Ib and IIb of the Periodic Table, wherein the ratio of (ii) to (iii) ranges from at least 1.66 : 1 by weight, said NOx reduction composition being (1) an integral component of the catalyst composition particles, (2) separate particles from the catalyst component or (3) mixtures of (1) and (2) and being present in the cracking catalyst in a sufficient NOx reducing amount.
13. The cracking catalyst of claim 12 wherein said cracking catalyst comprises an admixture of component (a) and component (b).
14. The cracking catalyst of claim 12 wherein said cracking catalyst comprises integral particles which contain both component (a) and component (b).
15. The cracking catalyst of claim 12 wherein the NOx reduction composition (b) comprises 0.1 to 15 wt % of the cracking catalyst composition.
16. The cracking catalyst of claim 12 wherein said oxide of a lanathnide series element other than ceria is praseodymium oxide.
17. A method of reducing NOx emission during fluid catalytic cracking of a hydrocarbon feedstock into lower molecular weight hydrocarbon components said method comprising contacting said hydrocarbon feedstock with a cracking catalyst suitable for catalyzing the cracking of hydrocarbons at elevated temperature whereby said lower molecular weight hydrocarbon components are formed in the presence of a NOx reduction composition, wherein said NOx reduction composition comprises (i) an acidic oxide support, (ii) at least 0.5 part by weight of cerium oxide per 100 parts by weight of acidic oxide support, (iii) at least one oxide of a lanthanide series element other than ceria and (iv) an oxide of a transition metal selected from Groups Ib and IIb of the Periodic Table, said NOx reduction component being present in a sufficient NOx reducing amount, wherein the ratio of (ii) to (iii) ranges from at least 1.66 : 1 by weight.
18. The method of claim 17 wherein said cracking catalyst and NOx reduction composition comprises an admixture of separate cracking catalyst component and the NOx reduction composition component.
19. The method of claim 17 wherein said cracking catalyst and NOx reduction composition comprises an integral combination of the cracking catalyst component and the NOx reduction composition component.
20. The method of claim 17 wherein said cracking catalyst is fluidized during contact with said hydrocarbon feedstock.
21. The method of claim 20 further comprising recovering used cracking catalyst from said contacting step and treating said used catalyst under conditions to regenerate said catalyst.
22. The method of claim 17 wherein said hydrocarbon feedstock contains at least 0.1 wt % nitrogen.
23. The method of claim 17 wherein said at least oxide of a lanthanide series element other than ceria is praseodymium oxide.
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US10/001,485 US6800586B2 (en) | 2001-11-23 | 2001-11-23 | NOx reduction composition for use in FCC processes |
US10/001,485 | 2001-11-23 | ||
PCT/US2002/035462 WO2003046112A1 (en) | 2001-11-23 | 2002-11-05 | Nox reduction composition for use in fcc processes |
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US (3) | US6800586B2 (en) |
EP (1) | EP1446462B1 (en) |
JP (1) | JP4443226B2 (en) |
KR (1) | KR100998819B1 (en) |
AU (1) | AU2002342336B2 (en) |
CA (1) | CA2468152C (en) |
MY (1) | MY134248A (en) |
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WO (1) | WO2003046112A1 (en) |
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-
2001
- 2001-11-23 US US10/001,485 patent/US6800586B2/en not_active Expired - Lifetime
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2002
- 2002-11-05 KR KR1020047007770A patent/KR100998819B1/en active IP Right Grant
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- 2002-11-05 EP EP02776460.4A patent/EP1446462B1/en not_active Expired - Lifetime
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- 2002-11-11 TW TW091133060A patent/TWI281875B/en active
- 2002-11-19 MY MYPI20024316A patent/MY134248A/en unknown
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US20040141897A1 (en) | 2004-07-22 |
EP1446462A1 (en) | 2004-08-18 |
TW200300364A (en) | 2003-06-01 |
EP1446462B1 (en) | 2015-03-18 |
AU2002342336A1 (en) | 2003-06-10 |
JP2005510356A (en) | 2005-04-21 |
CA2468152A1 (en) | 2003-06-05 |
US6852298B2 (en) | 2005-02-08 |
JP4443226B2 (en) | 2010-03-31 |
US20030098259A1 (en) | 2003-05-29 |
TWI281875B (en) | 2007-06-01 |
US7045485B2 (en) | 2006-05-16 |
US6800586B2 (en) | 2004-10-05 |
US20040141898A1 (en) | 2004-07-22 |
WO2003046112A1 (en) | 2003-06-05 |
KR100998819B1 (en) | 2010-12-06 |
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AU2002342336B2 (en) | 2008-05-29 |
KR20040055810A (en) | 2004-06-26 |
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