CN106807372A - A kind of catalyst for reducing regeneration fume from catalytic cracking pollutant emission and its application - Google Patents
A kind of catalyst for reducing regeneration fume from catalytic cracking pollutant emission and its application Download PDFInfo
- Publication number
- CN106807372A CN106807372A CN201710145467.9A CN201710145467A CN106807372A CN 106807372 A CN106807372 A CN 106807372A CN 201710145467 A CN201710145467 A CN 201710145467A CN 106807372 A CN106807372 A CN 106807372A
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- microsphere particle
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- oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000011069 regeneration method Methods 0.000 title claims abstract description 28
- 230000008929 regeneration Effects 0.000 title claims abstract description 27
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 25
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 22
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 22
- 239000003517 fume Substances 0.000 title claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 257
- 239000004005 microsphere Substances 0.000 claims abstract description 238
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003546 flue gas Substances 0.000 claims abstract description 26
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 16
- 150000002739 metals Chemical class 0.000 claims abstract description 11
- 238000005360 mashing Methods 0.000 claims description 34
- 239000002002 slurry Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000009938 salting Methods 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910003978 SiClx Inorganic materials 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000011806 microball Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 37
- 239000000243 solution Substances 0.000 description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- 239000000203 mixture Substances 0.000 description 25
- 238000003756 stirring Methods 0.000 description 25
- 239000000395 magnesium oxide Substances 0.000 description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 230000032683 aging Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 13
- 235000018660 ammonium molybdate Nutrition 0.000 description 13
- 229910001593 boehmite Inorganic materials 0.000 description 13
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 13
- 238000001694 spray drying Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910000420 cerium oxide Inorganic materials 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 12
- 150000002823 nitrates Chemical class 0.000 description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 12
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 12
- 238000012216 screening Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 229910001930 tungsten oxide Inorganic materials 0.000 description 12
- 239000000084 colloidal system Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 9
- 239000000571 coke Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000005995 Aluminium silicate Substances 0.000 description 7
- 235000012211 aluminium silicate Nutrition 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 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 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- OTCVAHKKMMUFAY-UHFFFAOYSA-N oxosilver Chemical class [Ag]=O OTCVAHKKMMUFAY-UHFFFAOYSA-N 0.000 description 6
- 229910003445 palladium oxide Inorganic materials 0.000 description 6
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 6
- 229910001923 silver oxide Inorganic materials 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 235000019504 cigarettes Nutrition 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- -1 nitrogen-containing compound Chemical class 0.000 description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000009418 renovation Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910002676 Pd(NO3)2·2H2O Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical compound [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 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 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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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
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
-
- 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
- C10G11/182—Regeneration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of catalyst for reducing regeneration fume from catalytic cracking pollutant emission and its application.The catalyst includes microsphere particle A and microsphere particle B；Counted with the weight of microsphere particle A as 100%, the microsphere particle A is included：70 95% aluminum oxide, 0.1 10% silica, 1 15% oxide selected from least two metals in group vib, VIII and IB races, the oxide of 0.1 2% rare earth element；Preferably, the aluminum oxide is 80 90%, and the silica is 0.1 5.0%；Counted with the weight of microsphere particle B as 100%, the microsphere particle B is included：70 95% aluminum oxide, 1 20% oxide selected from least two metals in Group IIA, Group IVB, group vib and VIII, the oxide of 0.1 2% rare earth element；Preferably, the aluminum oxide is 80 90%.The catalyst can reduce the discharge of NOx pollutants in regenerated flue gas.
Description
Technical field
The present invention relates to a kind of catalyst for reducing regeneration fume from catalytic cracking pollutant emission.
Background technology
Fluid catalytic cracking (hereinafter referred to as FCC) device is one of important heavy oil lighting device of oil plant, is production
The core apparatus of light oil particularly high-knock rating gasoline, are also the important process for producing the Organic Chemicals such as low-carbon alkene.
But containing a certain amount of NOx etc. to the disagreeableness contaminant gases of environment in FCC regenerated flue gas.According to statistics, oil refining enterprise row
The 10% of total release in the NOx difference duty gas put, the overwhelming majority therein comes from FCC apparatus.
NOx in FCC regenerated flue gas is mainly derived from the nitrogen-containing compound in feedstock oil.In FCC riser reactors,
While feedstock oil cracking, the small part coke laydown of generation inactivates it in catalyst surface, and part nitrogen enters coke,
When catalyst coke burning regeneration process is carried out in FCC regenerators, nitrogen oxidation transformation is discharged into greatly into NOx with regenerated flue gas
In gas.During cracking reaction, basic nitrogen compound is adsorbed on the acid centre of catalyst and forms coke, and neutral
Nitrogen compound is then considered as entering in product, and the nitrogen in raw material close to half enters coke.In catalyst regeneration burning process,
Nitrogen on coke is only had 3%-25% and is entered flue gas in the form of NO, and remaining is then converted into N2Form exist.FCC regenerates cigarette
The concentration of NOx is 0.005v%-0.05v%, mainly NO (about 90%) in gas, and a small amount of NO is contained simultaneously2(about 10%).
At present, the flue gas denitrification and measure for the complete combustive regeneration mode of catalytic cracking mainly include：
1) feedstock oil hydrodenitrogeneration, the method can be effectively reduced NOx emission, and energy improve product quality, deficiency
Place be hydrogenation plant capital construction and operating cost it is all higher.
2) renovation process is changed, the catalysis of reclaimable catalyst distributor designs Cheng Rangfu carbon in the design of counter-current regeneration device
Agent is uniformly distributed along bed face, so as to be reduced to leaving the NOx in bed flue gas, for example with Kellog adverse currents again
Raw device or multistage regenerator, but the transformation of regenerator needs substantial amounts of fund input.
3) denitration process are carried out to regenerated flue gas outside FCC apparatus, i.e., makees reducing agent using ammonia, in the feelings that oxygen is present
Under condition, by V2O5/TiO2Deng the catalytic action of catalyst, nitrogen oxides is reduced to nitrogen, the nitrogen oxidation in flue gas can be made
Thing is reduced to very low level, but simultaneously excessive NH3And oxidation side reaction can make to increase a small amount of SO in flue gas3, so as to produce
Secondary pollution problem, influences its efficiency.
4) denitrating catalyst is used, the method is that a certain amount of auxiliary agent is added during FCC, makes to be produced in regenerative process
NOx be reduced or be directly decomposed into N2, so as to reduce the discharge of NOx in regenerated flue gas, and can effectively take precautions against CO tails
Combustion.It is small investment, easy to use due to using catalyst appliance arrangement structure need not be changed, therefore the method increasingly receives
To the attention of people.
In the prior art, the NOx in mainly being removed smoke by two kinds of principles.
I () is directly degraded NO, that is, is not needed additional reducing agent, directly NO is dissociated into N by metal catalytic2And O2But,
Reaction activity is built very high；Copper is one is preferably used for the catalyst activity constituent element that NO directly dissociates, but easily makes
Into the poisoning of catalytic cracking host, product slates are deteriorated.
(ii) SCR, by reducing agent (such as CO, hydrocarbon HC or C) in transition metal
The lower reduction NO of effect, this is the method that most of auxiliary agent designs are used at present；But under the conditions of complete combustive regeneration, reducing agent CO
Concentration it is very low, limit auxiliary agent and play a role.
Prior art serves certain effect to the content for reducing the NOx in catalytic cracking flue gas, but for catalysis
There is the following aspects in the complete combustive regeneration flue gas reduction NOx content of cracking, current catalyst：As CO in flue gas
When concentration is too low, there is reduction reaction and be greatly reduced in CO and NO, and the de- NOx effects of auxiliary agent are poor；Make when copper, nickel etc. is used in auxiliary agent
During for active component, the poisoning of catalytic cracking host is easily caused, hydrogen content rises in catalytic cracked dry gas, and coke yield increases
(catalytic cracking process and engineering, Chen Junwu, Sinopec publishing house, 2005：310-319).Therefore, existing catalytic cracking cigarette
The auxiliary agent of qi exhaustion NOx, during for complete combustive regeneration, performance needs further raising.
The content of the invention
In order to solve the above technical problems, reducing regeneration fume from catalytic cracking pollutant row it is an object of the invention to provide one kind
The catalyst put and its application, reduce the discharge of NOx pollutants in regenerated flue gas.
In order to achieve the above object, the invention provides a kind of catalysis for reducing regeneration fume from catalytic cracking pollutant emission
Agent, the catalyst includes microsphere particle A and microsphere particle B；
Counted with the weight of microsphere particle A as 100%, microsphere particle A is included：The aluminum oxide of 70-95%, the oxygen of 0.1-10%
SiClx, the oxide selected from least two metals in group vib, VIII and IB races of 1-15%, the rare earth element of 0.1-2%
Oxide；
Counted with the weight of microsphere particle B as 100%, microsphere particle B is included：The aluminum oxide of 70-95%, 1-20%'s is selected from
The oxide of at least two metals in Group IIA, Group IVB, group vib and VIII, the oxide of the rare earth element of 0.1-2%.
In above-mentioned catalyst, it is preferable that in microsphere particle A, the content of aluminum oxide is 80-90%, and silica contains
It is 0.1-5.0% to measure；In microsphere particle B, the content of aluminum oxide is 80-90%.
In above-mentioned catalyst, it is preferable that the weight ratio of microsphere particle A and microsphere particle B is (0.01-10):1.
In above-mentioned catalyst, it is preferable that the heap density of microsphere particle A is 0.85-1.00g/mL, the heap of microsphere particle B
Density is 0.75-0.85g/mL.
In above-mentioned catalyst, it is preferable that the sieve of microsphere particle A is grouped into 0-20 μm<0.1 weight %, microsphere particle B
Sieve be grouped into 0-20 μm<4.0 weight %.
In above-mentioned catalyst, it is preferable that in microsphere particle A, the metal in group vib is the one kind or two in Mo and W
The combination planted, the percentage by weight of its oxide is no more than the 10% of microsphere particle A；
Metal in VIII is one or two the combination in Co and Pd, and the percentage by weight of its oxide is no more than
The 3% of microsphere particle A；
Metal in IB races is Ag, and the percentage by weight of its oxide is no more than the 3% of microsphere particle A；
Above-mentioned rare earth element is Ce, and the percentage by weight of its oxide accounts for the 0.8-2% of microsphere particle A.
In above-mentioned catalyst, it is preferable that in microsphere particle B, the metal in Group IIA is Mg, the weight of its oxide
15% of percentage no more than microsphere particle B；
Metal in Group IVB is Zr, and the percentage by weight of its oxide is no more than the 5% of microsphere particle B；
Metal in group vib is one or two the combination in Mo and W, and the percentage by weight of its oxide is no more than micro-
The 10% of ball particle B；
Metal in VIII is one or two the combination in Co and Pd, and the percentage by weight of its oxide is no more than
The 3% of microsphere particle B；
Above-mentioned rare earth element is Ce, and the percentage by weight of its oxide accounts for the 0.8-1.6% of microsphere particle B.
Metal or rare earth element in each race include but is not limited to above-mentioned specific metal.
In above-mentioned catalyst, it is preferable that microsphere particle A is prepared by following steps：Aluminum oxide group will be contained
The silicon source divided mixes mashing with the silicon source containing silica component, controls slurries pH, then is spray-dried, is calcined, and obtains microballoon
Grain carrier, by microsphere particle carrier with the salting liquid selected from least two metals in VB races, group vib, VIII and IB races and
Metal salt solution dipping containing rare earth element, microsphere particle A is obtained after drying, roasting；
In above-mentioned catalyst, it is preferable that microsphere particle B is prepared by following steps：Aluminum oxide group will be contained
The silicon source divided is beaten, and controls slurries pH, is subsequently adding selected from least two in Group IIA, Group IVB, group vib and VIII
The oxide of metal, mixing mashing, then is spray-dried, is calcined, and obtains microsphere particle carrier, by microsphere particle carrier with being selected from
The salting liquid and the salt solution impregnation containing rare earth element of at least two metals in Group IIA, Group IVB, group vib and VIII,
Microsphere particle B is obtained after drying, roasting.
In above-mentioned catalyst, it is preferable that it is 1.2-2.0 to control slurries pH；Dry temperature is 120-280 DEG C, is dried
Time be 1-3 hours；Preferably, dry temperature is 180-200 DEG C, and the dry time is 1-2 hours；
The temperature of roasting is 500-800 DEG C, time 1-4 hours of roasting；Preferably, the temperature of roasting is 600-700 DEG C,
The time of roasting is 2-3 hours.
In the preparation method of microsphere particle A and microsphere particle B, mashing plastic, spray drying, dipping, drying, roasting,
Method for sieving is conventional catalyst process technology, does not have particular/special requirement.
Above-mentioned catalyst can apply to reduce the discharge of nitrogen-containing pollutant, it is preferable that the catalyst is with (1:99)-(6:
94) ratio is used in mixed way with industrial poising agent.
The characteristics of present invention coexists according to NOx in regenerator dense-phase bed and CO, NOx reducing agents are made with CO, there is provided a kind of
Heap density is distributed in fluid bed dense-phase bed probability slightly larger than the microsphere particle A of FCC catalyst using the big microsphere particle of heap density
Big characteristic, selects suitable active component it is had catalysis activity high to the reaction between NOx and CO in dense-phase bed
And selectivity；The microsphere particle B that a kind of heap density is slightly less than FCC catalyst is provided simultaneously, using heap density minimicrosphere particle point
Cloth in the big characteristic of fluid bed dilute phase bed probability, select suitable active component make its in dilute phase bed to CO burnings and
Reaction between NOx and CO plays a role simultaneously；To the two kinds of microsphere particle A and microsphere particle B that provide, according in regenerated flue gas
The combustion case of CO is mixed to form catalyst according to different ratios in NOx pollutant loads and regenerator, in FCC regenerators
Using the reaction that can respectively strengthen the removing NOx that dilute, dense-phase bed occurs, CO has been reached combustion-supporting and substantially reduce regenerated flue gas
Middle NOxThe purpose of pollutant emission.
Can be by the NOx in regenerated flue gas from 500mg/m using above-mentioned catalyst in FCC apparatus3It is reduced to 97mg/m3, take off
Except rate reaches 80.6%；CO contents in flue gas reduce 9.07% compared with using Pt combustion adjuvants；And the addition of catalyst is right
FCC total liquid yields and light receipts have no adverse effect, and the yield of main purpose product is basically unchanged.
Compared with existing catalyst, catalyst of the invention has preferably reduces NO in regenerated flue gasxIt is combustion-supporting with CO
Catalytic effect, reduces NO in flue gas under particularly complete combustive regeneration operator schemexThe concentration of atmosphere pollution, and will not be right
FCC product yields are adversely affected.Complete combustive regeneration operator scheme of the invention is one kind of existing catalytic cracking unit
Conventional regeneration processes.Renovation process can be found in《Catalytic cracking process and engineering》(Chen Junwu is edited, Sinopec publishing house 2005
Year publishes) the 1260-1343 pages.
Specific embodiment
In order to be more clearly understood to technical characteristic of the invention, purpose and beneficial effect, now to skill of the invention
Art scheme carry out it is described further below, but it is not intended that to it is of the invention can practical range restriction.
Raw materials used in each embodiment is the slaine of market sale, for example cobalt nitrate (Co (NO3)2·6H2O) it is Tianjin
The production of recovery development in science and technology Co., Ltd of city；Silver nitrate (AgNO3) it is the production of Zhengzhou Hua Mao chemical products Co., Ltd；Palladium nitrate
(Pd(NO3)2·2H2O) it is the production of Tianjin recovery fine chemistry industry research institute；Cerous nitrate (Ce (NO3)3·6H2O) for Zibo is auspicious rich
Health rare earth material Co., Ltd produces；Or market sale is solvable with water and heat resolve turns into the metallic salt of oxide, for example
Ammonium metatungstate ((NH4)6W7O24·6H2O) for analysis is pure, Chemical Reagent Co., Ltd., Sinopharm Group's production；Ammonium niobium oxalate (NH4
[NbO(C2O4)2]) content is more than 99.99%, is the limited public production of the red profit Information technology in Luoyang；Ammonium molybdate ((NH4)6Mo7O24·4
(H2O)) for analysis is pure, the production of Shanghai Aladdin biochemical technology limited company；Zirconium oxide (ZrO2) it is the brilliant auspicious new material in Xuancheng
Co., Ltd produces；The boehmite (the wherein weight % of alumina content 60) of Shandong Aluminium Industrial Corp's production；Kaolin is Soviet Union
State China Kaolin Co., Ltd produces (SiO2The weight % of content 56), hydrochloric acid (the weight % of concentration 36.5, chemistry is pure) used, Beijing
Plant produced；Calcium oxide (CaO) produce for Hubei heart Yin He Chemical Co., Ltd.s (>The weight % of content 98)；Magnesia (MgO) is
Weifang Xu Hui new materials Co., Ltd produce (>The weight % of content 98).
Embodiment 1
A kind of catalyst for reducing regeneration fume from catalytic cracking pollutant emission is present embodiments provided, the catalyst is included
Microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by following steps：
Deionized water is added in stirred tank, 1.591 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.081 kilogram of kaolin is added in stirred tank, is beaten about 60 minutes；60-80 DEG C is heated to, is stood aging about 120 minutes
And continue stirring 30 minutes, the colloid material after mashing is then obtained into microsphere particle carrier with spray drying system is pumped into,
Microsphere particle carrier is calcined 120 minutes at 700 DEG C, 1 kilogram of microsphere particle carrier is obtained, the composition of the microsphere particle carrier contains
The weight % of aluminum oxide 95.45, the weight % of silica 4.55.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 92.9 grams of ammonium metatungstates, 28 grams of ammonium molybdates, 50.3 grams
Silver nitrate, 2.88 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 are impregnated with solution saturation
DEG C drying 120 minutes, 700 DEG C be calcined 120 minutes, obtain microsphere particle A.
Screening microsphere particle A, makes microsphere particle A sieve composition containing 0-20 μm of particle<0.1 weight %.Finally, microballoon
The heap density of grain A is 0.9g/mL, and the composition of microsphere particle A contains 83.9 weight % aluminum oxide, 4.0 weight % silica, 7 weights
Amount % tungsten oxides, 2.0 weight % molybdenum oxides, 3.0 weight % silver oxides, 0.1 weight % cerium oxide.
Wherein, microsphere particle B is prepared by following steps：
Deionized water is added in stirred tank, 1.574 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.057 kilogram of magnesia is added in stirred tank, is beaten about 60 minutes；70-90 DEG C is heated to, is stood aging about 120 minutes
And continue stirring 30 minutes, the colloid material after mashing is then obtained into microsphere particle carrier with spray drying system is pumped into,
Microsphere particle carrier is calcined 120 minutes at 600 DEG C, 1 kilogram of microsphere particle carrier is obtained, microsphere particle carrier composition is oxygen-containing
Change the weight % of aluminium 94.44, the weight % of magnesia 5.56.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 38.9 grams of ammonium metatungstates, 41.0 grams of ammonium molybdates, 86.8
Gram cobalt nitrate, 1.46 grams of palladium nitrates, 56.4 grams of cerous nitrates are configured to solution respectively, stir.Microballoon is impregnated with solution saturation
Particulate vector, then dries 120 minutes for 180 DEG C, is calcined 120 minutes at 700 DEG C, obtains microsphere particle B.
Screening microsphere particle B, makes microsphere particle B sieve composition containing 0-20 μm of particle<4 weight %.Finally, microsphere particle
The heap density of B is 0.8g/mL, and the composition of microsphere particle B contains 84.94 weight % aluminum oxide, 5.0 weight % magnesia, 3.0 weights
Amount % tungsten oxides, 3.0 weight % molybdenum oxides, 2.0 weight % cobalt oxides, the weight % of palladium oxide 0.06,2.0 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B is 1 in the catalyst:1.
Embodiment 2
A kind of catalyst for reducing regeneration fume from catalytic cracking pollutant emission is present embodiments provided, the catalyst is included
Microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by following steps：
Deionized water is added in stirred tank, 1.665 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.0019 kilogram of kaolin is added in stirred tank, is beaten about 60 minutes；60-80 DEG C is heated to, is stood aging about 120 minutes
And continue stirring 30 minutes, the colloid material after mashing is then obtained into microsphere particle carrier with spray drying system is pumped into,
Microsphere particle carrier is obtained into 1 kilogram of microsphere particle carrier for 120 minutes in 700 DEG C of roastings, the microsphere particle carrier is salic
99.89 weight %, the weight % of silica 0.11.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 62.6 grams of ammonium metatungstates, 13.2 grams of ammonium molybdates, 1.6 grams
Silver nitrate, 21.8 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 are impregnated with solution saturation
DEG C drying 120 minutes, 700 DEG C be calcined 120 minutes, obtain microsphere particle A.
Screening microsphere particle A, makes microsphere particle A sieve the particle for being grouped into 0-20 μm<0.1 weight %.Finally, microballoon
The heap density of grain A is 0.9g/mL, and the composition of microsphere particle A contains 93.0 weight % aluminum oxide, 0.1 weight % silica, 5.0 weights
Amount % tungsten oxides, 1.0 weight % molybdenum oxides, 0.1 weight % silver oxides, 0.8 weight % cerium oxide.
Wherein, microsphere particle B is prepared by following steps：
Deionized water is added in stirred tank, 1.363 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes, continued
0.16 kilogram of magnesia is added in stirred tank, is beaten about 60 minutes；Continue to add 26.1 grams of zirconium oxide in stirred tank, mashing is about
60 minutes；70-90 DEG C is heated to, aging about 120 minutes is stood and is continued stirring 30 minutes, then by the colloid after mashing
Material obtains microsphere particle carrier with spray drying system is pumped into, and microsphere particle carrier is calcined 120 minutes at 600 DEG C, obtains
To 1 kilogram of microsphere particle carrier, the microsphere particle carrier constitute salic 81.76 weight %, the weight % of magnesia 15.63,
The weight % of zirconium oxide 2.61.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 18.2 grams of ammonium metatungstates, 25.6 grams of ammonium molybdates, 0.9 gram
Palladium nitrate, 13.2 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 are impregnated with solution saturation
DEG C drying 120 minutes, obtain microsphere particle B within 120 minutes in 700 DEG C of roastings.
Screening microsphere particle B, makes microsphere particle B sieve the particle for being grouped into 0-20 μm<4 weight %.Finally, microsphere particle
The heap density of B is 0.8g/mL, and the composition of microsphere particle B contains 78.46 weight % aluminum oxide, 15.0 weight % magnesia, 1.5 weights
Amount % tungsten oxides, 2.0 weight % molybdenum oxides, the weight % of palladium oxide 0.04,0.5 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B is 1 in the catalyst:1.
Embodiment 3
A kind of catalyst for reducing regeneration fume from catalytic cracking pollutant emission is present embodiments provided, the catalyst is included
Microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by following steps：
Deionized water is added in stirred tank, 1.476 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.204 kilogram of kaolin is added in stirred tank, is beaten about 60 minutes；60-80 DEG C is heated to, is stood aging about 120 minutes
And continue stirring 30 minutes, the colloid material after mashing is then obtained into microsphere particle carrier with spray drying system is pumped into,
Microsphere particle carrier is calcined 120 minutes at 700 DEG C, 1 kilogram of microsphere particle carrier is obtained, the microsphere particle carrier is salic
88.57 weight %, the weight % of silica 11.43.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 120 grams of ammonium metatungstates, 14.1 grams of ammonium molybdates, 16.8 grams
Silver nitrate, 43.5 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 are impregnated with solution saturation
DEG C drying 120 minutes, be that 700 DEG C of roastings obtain microsphere particle A in 120 minutes.
Screening microsphere particle A, makes microsphere particle A sieve the particle of 0-20 μm of composition<0.1 weight %.Final microsphere particle A
Heap density be 0.9g/mL, the composition of microsphere particle A contains 77.50 weight % aluminum oxide, 10.0 weight % silica, 9 weight %
Tungsten oxide, 1.0 weight % molybdenum oxides, 1.0 weight % silver oxides, 1.5 weight % cerium oxide.
Wherein, microsphere particle B is prepared by following steps：
Deionized water is added in stirred tank, 1.567 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.011 kilogram of magnesia is added in stirred tank, is beaten about 60 minutes；Continue to add 48.7 grams of zirconium oxide in stirred tank, mashing
About 60 minutes；70-90 DEG C is heated to, aging about 120 minutes is stood and is continued stirring 30 minutes, then by the glue after mashing
Body material obtains microsphere particle carrier with spray drying system is pumped into, and microsphere particle carrier is calcined 120 minutes at 600 DEG C,
Obtain 1 kilogram of microsphere particle carrier, the microsphere particle carrier constitute salic 94.05 weight %, the weight % of magnesia 1.08,
The weight % of zirconium oxide 4.87.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 56.8 grams of ammonium metatungstates, 26.6 grams of ammonium molybdates, 1.66
Gram palladium nitrate, 27.4 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier is impregnated with solution saturation, then
180 DEG C are dried 120 minutes, and microsphere particle B is obtained within 120 minutes in 700 DEG C of roastings.
Screening microsphere particle B, makes microsphere particle B sieve the particle for being grouped into 0-20 μm<4 weight %.Finally, microsphere particle
The heap density of B is 0.8g/mL, and the composition of microsphere particle B contains 86.93 weight % aluminum oxide, 1.0 weight % magnesia, zirconium oxide
4.5 weight %, 4.5 weight % tungsten oxides, 2.0 weight % molybdenum oxides, the weight % of palladium oxide 0.07,1.0 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B is 1 in the catalyst:1.
Embodiment 4
A kind of catalyst for reducing regeneration fume from catalytic cracking pollutant emission is present embodiments provided, the catalyst is included
Microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by following steps：
Deionized water is added in stirred tank, 1.476 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.204 kilogram of kaolin is added in stirred tank, is beaten about 60 minutes；60-80 DEG C is heated to, is stood aging about 120 minutes
And continue stirring 30 minutes, the colloid material after mashing is then obtained into microsphere particle carrier with spray drying system is pumped into,
Microsphere particle carrier is calcined 120 minutes at 700 DEG C, 1 kilogram of microsphere particle carrier is obtained, the microsphere particle carrier is salic
88.57 weight %, the weight % of silica 11.43.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 120 grams of ammonium metatungstates, 14.1 grams of ammonium molybdates, 16.8 grams
Silver nitrate, 43.5 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 are impregnated with solution saturation
DEG C drying 120 minutes, be that 700 DEG C of roastings obtain microsphere particle A in 120 minutes.
Screening microsphere particle A, makes microsphere particle A sieve the particle of 0-20 μm of composition<0.1 weight %.Final microsphere particle A
Heap density be 0.9g/mL, the composition of microsphere particle A contains 77.50 weight % aluminum oxide, 10.0 weight % silica, 9 weight %
Tungsten oxide, 1.0 weight % molybdenum oxides, 1.0 weight % silver oxides, 1.5 weight % cerium oxide.
Wherein, microsphere particle B is prepared by following steps：
Deionized water is added in stirred tank, 1.574 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.057 kilogram of magnesia is added in stirred tank, is beaten about 60 minutes；Mashing about 60 minutes；70-90 DEG C is heated to, is stood
Aging about 120 minutes and continue stirring 30 minutes, then the colloid material after mashing is obtained with spray drying system is pumped into
Microsphere particle carrier, microsphere particle carrier is calcined 120 minutes at 600 DEG C, obtains 1 kilogram of microsphere particle carrier, the microballoon
Grain carrier constitutes salic 94.44 weight %, the weight % of magnesia 5.56.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 38.9 grams of ammonium metatungstates, 41.0 grams of ammonium molybdates, 86.8
Gram cobalt nitrate, 1.46 grams of palladium nitrates, 56.4 grams of cerous nitrates are configured to solution respectively, stir.Microballoon is impregnated with solution saturation
Particulate vector, is then dried 120 minutes for 180 DEG C, and microsphere particle B is obtained within 120 minutes in 700 DEG C of roastings.
Screening microsphere particle B, makes microsphere particle B sieve composition containing 0-20 μm of particle<4 weight %.Finally, microsphere particle
The heap density of B is 0.8g/mL, and the composition of microsphere particle B contains 84.94 weight % aluminum oxide, 5.0 weight % magnesia, 3.0 weights
Amount % tungsten oxides, 3.0 weight % molybdenum oxides, 2.0 weight % cobalt oxides, the weight % of palladium oxide 0.06,2.0 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B is 4 in the catalyst:6.
Embodiment 5
A kind of catalyst for reducing regeneration fume from catalytic cracking pollutant emission is present embodiments provided, the catalyst is included
Microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by following steps：
Deionized water is added in stirred tank, 1.476 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.204 kilogram of kaolin is added in stirred tank, is beaten about 60 minutes；60-80 DEG C is heated to, is stood aging about 120 minutes
And continue stirring 30 minutes, the colloid material after mashing is then obtained into microsphere particle carrier with spray drying system is pumped into,
Microsphere particle carrier is calcined 120 minutes at 700 DEG C, 1 kilogram of microsphere particle carrier is obtained, the microsphere particle carrier is salic
88.57 weight %, the weight % of silica 11.43.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 120 grams of ammonium metatungstates, 14.1 grams of ammonium molybdates, 16.8 grams
Silver nitrate, 43.5 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 are impregnated with solution saturation
DEG C drying 120 minutes, obtain microsphere particle A within 120 minutes in 700 DEG C of roastings.
Screening microsphere particle A, makes microsphere particle A sieve the particle of 0-20 μm of composition<0.1 weight %.Final microsphere particle A
Heap density be 0.9g/mL, the composition of microsphere particle A contains 77.50 weight % aluminum oxide, 10.0 weight % silica, 9 weight %
Tungsten oxide, 1.0 weight % molybdenum oxides, 1.0 weight % silver oxides, 1.5 weight % cerium oxide.
Wherein, microsphere particle B is prepared by following steps：
Deionized water is added in stirred tank, 1.363 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.16 kilogram of magnesia is added in stirred tank, is beaten about 60 minutes；Continue to add 26.1 grams of zirconium oxide in stirred tank, mashing is about
60 minutes；70-90 DEG C is heated to, aging about 120 minutes is stood and is continued stirring 30 minutes, then by the colloid after mashing
Material obtains microsphere particle carrier with spray drying system is pumped into, and microsphere particle carrier is calcined 120 minutes at 600 DEG C, obtains
To 1 kilogram of microsphere particle carrier, the microsphere particle carrier constitute salic 81.76 weight %, the weight % of magnesia 15.63,
The weight % of zirconium oxide 2.61.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 18.2 grams of ammonium metatungstates, 25.6 grams of ammonium molybdates, 0.9 gram
Palladium nitrate, 13.2 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 are impregnated with solution saturation
DEG C drying 120 minutes, be that 700 DEG C of roastings obtain microsphere particle B in 120 minutes.
Screening microsphere particle B, makes microsphere particle B sieve the particle for being grouped into 0-20 μm<4 weight %.Finally, microsphere particle
The heap density of B is 0.8g/mL, and the composition of microsphere particle B contains 78.46 weight % aluminum oxide, 15.0 weight % magnesia, 1.5 weights
Amount % tungsten oxides, 2.0 weight % molybdenum oxides, the weight % of palladium oxide 0.04,0.5 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B is 4 in the catalyst:6.
Embodiment 6
A kind of catalyst for reducing regeneration fume from catalytic cracking pollutant emission is present embodiments provided, the catalyst is included
Microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by following steps：
Deionized water is added in stirred tank, 1.591 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue in stirring
0.081 kilogram of kaolin is added in kettle, is beaten about 60 minutes；Be heated to 60-80 DEG C, stand aging about 120 minutes and after
Continuous stirring 30 minutes, then obtains microsphere particle carrier by the colloid material after mashing with spray drying system is pumped into, will be micro-
Ball particle carrier is calcined 120 minutes at 700 DEG C, obtains 1 kilogram of microsphere particle carrier, and the composition of the microsphere particle carrier is containing oxidation
The weight % of aluminium 95.45, the weight % of silica 4.55.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 92.9 grams of ammonium metatungstates, 28 grams of ammonium molybdates, 50.3 grams
Silver nitrate, 2.88 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 are impregnated with solution saturation
DEG C drying 120 minutes, 700 DEG C be calcined 120 minutes, obtain microsphere particle A.
Screening microsphere particle A, makes microsphere particle A sieve composition containing 0-20 μm of particle<0.1 weight %.Finally, microballoon
The heap density of grain A is 0.9g/mL, and the composition of microsphere particle A contains 83.9 weight % aluminum oxide, 4.0 weight % silica, 7 weights
Amount % tungsten oxides, 2.0 weight % molybdenum oxides, 3.0 weight % silver oxides, 0.1 weight % cerium oxide.
Wherein, microsphere particle B is prepared by following steps：
Deionized water is added in stirred tank, 1.363 kilograms of mashing of boehmite are subsequently adding, slurry solid content is controlled
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, slurries pH=1.2-2.0 is controlled, is beaten about 60 minutes；Continue
0.16 kilogram of magnesia is added in stirred tank, is beaten about 60 minutes；Continue to add 26.1 grams of zirconium oxide in stirred tank, mashing is about
60 minutes；70-90 DEG C is heated to, aging about 120 minutes is stood and is continued stirring 30 minutes, then by the colloid after mashing
Material obtains microsphere particle carrier with spray drying system is pumped into, and microsphere particle carrier is calcined 120 minutes at 600 DEG C, obtains
To 1 kilogram of microsphere particle carrier, the microsphere particle carrier constitute salic 81.76 weight %, the weight % of magnesia 15.63,
The weight % of zirconium oxide 2.61.
On the basis of according to 1 kilogram of microsphere particle carrier (butt), by 18.2 grams of ammonium metatungstates, 25.6 grams of ammonium molybdates, 0.9 gram
Palladium nitrate, 13.2 grams of cerous nitrates are configured to solution respectively, stir.Microsphere particle carrier, then 180 are impregnated with solution saturation
DEG C drying 120 minutes, be 700 DEG C be calcined 120 minutes, obtain microsphere particle B.
Screening microsphere particle B, makes microsphere particle B sieve the particle for being grouped into 0-20 μm<4 weight %.Finally, microsphere particle
The heap density of B is 0.8g/mL, and the composition of microsphere particle B contains 78.46 weight % aluminum oxide, 15.0 weight % magnesia, 1.5 weights
Amount % tungsten oxides, 2.0 weight % molybdenum oxides, the weight % of palladium oxide 0.04,0.5 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B is 4 in the catalyst:6.
Embodiment 7
A kind of catalyst for reducing regeneration fume from catalytic cracking pollutant emission is present embodiments provided, the catalyst is only wrapped
A containing microsphere particle.The preparation method of microsphere particle A is shown in embodiment 4.
Embodiment 8
A kind of catalyst for reducing regeneration fume from catalytic cracking pollutant emission is present embodiments provided, the catalyst is only wrapped
B containing microsphere particle.The preparation method of microsphere particle B is shown in embodiment 4.
Comparative example 1
The catalyst of the selection of comparative example 1 is the commodity for having been used to commercial Application in the prior art：(Shandong is pretty for CO combustion adjuvants
Fly Chemical Co., Ltd.).
Comparative example 2
The catalyst of the selection of comparative example 2 is the commodity for having been used to commercial Application in the prior art：LDN-1 (sinopec Lip rivers
Positive Engineering Co., Ltd).
Comparative example 3
The catalyst of the selection of comparative example 3 is the commodity for having been used to commercial Application in the prior art：FP-DN auxiliary agents (Beijing
Trimerization environmental friendly material limited company).
Experimental performance evaluation result
The chemical composition of the catalyst in each embodiment and comparative example is by x-ray fluorescence spectrometry.
Flue gas is analyzed with German MRU companies E8500 Portable smoke analysis instrument to constitute, including O2, NO, NOx, SOx, CO and
CO2Content.
The catalyst for being used for performance evaluation in each embodiment and comparative example need to be enterprising in fluid bed hydrothermal aging device in advance
Aging 10 hours of 800 DEG C of row, 100% vapor, then (sinopec catalyst Chang Ling branch company produces with FCC industry poising agent
CDC catalytic cracking catalysts) mixing, catalyst and FCC industry poising agent weight ratio are 3:97, urged in successive reaction-regeneration
Change and evaluated on the medium-sized experimental provision of cracking, 10 kilograms of catalyst loading amount, 500 DEG C of reaction temperature, catalyst regeneration temperature 700
℃。
1st, the raw material oil nature that the present invention is used is as shown in table 1.
Material density 0.921g/cm3, carbon residue 4.51wt%, S, N element composition are in higher level, are refinings at present
The typical case that factory uses urges raw material again.NOx and CO contents are higher in flue gas during catalyst regeneration process.
Table 1
2nd, catalyst and chemical composition are as shown in table 2.
Table 2
3rd, the catalyst in Application Example and comparative example, such as concentration of major pollutants and change in regenerated flue gas, table 3
It is shown.
Table 3
Embodiment 1-6 to reduce flue gas in NOx and CO all play a role, wherein, embodiment 4 compared with comparative example 1, cigarette
NOx and CO in gas reduce 80.6% and 8.14% respectively, show good removal effect.In embodiment 7 and 8,
A particles or B particles is used alone, has certain limitation respectively in terms of NOx and CO is removed, without the effect that performance is optimal
Really.
4th, the catalyst in embodiment and comparative example is as shown in table 4 to the performance of catalytic cracking product.
Table 4
The addition of all catalyst has little to no effect to product slates, wherein, the dry gas and coke yield of embodiment 3,4
It is lower slightly, better than other catalyst.
Claims (10)
1. it is a kind of reduce regeneration fume from catalytic cracking pollutant emission catalyst, the catalyst include microsphere particle A and microballoon
Particle B；
Counted with the weight of microsphere particle A as 100%, the microsphere particle A is included：The aluminum oxide of 70-95%, the oxygen of 0.1-10%
SiClx, the oxide selected from least two metals in group vib, VIII and IB races of 1-15%, the rare earth element of 0.1-2%
Oxide；Preferably, the content of the aluminum oxide is 80-90%, and the content of the silica is 0.1-5.0%；
Counted with the weight of microsphere particle B as 100%, the microsphere particle B is included：The aluminum oxide of 70-95%, 1-20%'s is selected from
The oxide of at least two metals in Group IIA, Group IVB, group vib and VIII, the oxide of the rare earth element of 0.1-2%；
Preferably, the content of the aluminum oxide is 80-90%.
2. catalyst as claimed in claim 1, wherein, the weight ratio of the microsphere particle A and microsphere particle B is (0.01-
10):1。
3. catalyst as claimed in claim 1 or 2, wherein, the heap density of the microsphere particle A is 0.85-1.00g/mL, institute
The heap density for stating microsphere particle B is 0.75-0.85g/mL.
4. the catalyst as any one of claim 1-3, wherein, the sieve of the microsphere particle A is grouped into 0-20 μm<
0.1 weight %, the sieve of the microsphere particle B is grouped into 0-20 μm<4.0 weight %.
5. the catalyst as any one of claim 1-4, wherein, in microsphere particle A：
Metal in the group vib is one or two the combination in Mo and W, and the percentage by weight of its oxide is no more than institute
State the 10% of microsphere particle A；
Metal in the VIII is one or two the combination in Co and Pd, and the percentage by weight of its oxide is no more than
The 3% of the microsphere particle A；
Metal in the IB races is Ag, and the percentage by weight of its oxide is no more than the 3% of the microsphere particle A；
The rare earth element is Ce, and the percentage by weight of its oxide accounts for the 0.8-2% of the microsphere particle A.
6. the catalyst as any one of claim 1-5, wherein, in microsphere particle B：
Metal in the Group IIA is Mg, and the percentage by weight of its oxide is no more than the 15% of the microsphere particle B；
Metal in the Group IVB is Zr, and the percentage by weight of its oxide is no more than the 5% of the microsphere particle B；
Metal in the group vib is one or two the combination in Mo and W, and the percentage by weight of its oxide is no more than institute
State the 10% of microsphere particle B；
Metal in the VIII is one or two the combination in Co and Pd, and the percentage by weight of its oxide is no more than
The 3% of the microsphere particle B；
The rare earth element is Ce, and the percentage by weight of its oxide accounts for the 0.8-1.6% of the microsphere particle B.
7. the catalyst as described in any one of claim 1-6, wherein, the microsphere particle A is prepared by following steps
Obtain：Silicon source containing alumina component is mixed into mashing with the silicon source containing silica component, slurries pH is controlled, then spray
Dry, be calcined, obtain microsphere particle carrier, by the microsphere particle carrier with selected from VB races, group vib, VIII and IB races
At least two metals salting liquid and containing the rare earth element metal salt solution dipping, through drying, roasting after obtain micro-
Ball particle A.
8. the catalyst as described in any one of claim 1-7, wherein, the microsphere particle B is prepared by following steps
Obtain：Silicon source containing alumina component is beaten, slurries pH is controlled, is subsequently adding selected from Group IIA, Group IVB, VIB
The oxide of at least two metals in race and VIII, mixing mashing, then be spray-dried, be calcined, microsphere particle carrier is obtained,
By the microsphere particle carrier is with the salting liquid selected from least two metals in Group IIA, Group IVB, group vib and VIII and contains
There is the salt solution impregnation of the rare earth element, microsphere particle B is obtained after drying, roasting.
9. catalyst as claimed in claim 7 or 8, wherein, the pH is 1.2-2.0；
The dry temperature is 120-280 DEG C, and the dry time is 1-3 hours；Preferably, the dry temperature is 180-
200 DEG C, the dry time is 1-2 hours；
The temperature of the roasting is 500-800 DEG C, time 1-4 hours of roasting；Preferably, the temperature of the roasting is 600-
700 DEG C, the time of roasting is 2-3 hours.
10. application of the catalyst any one of claim 1-9 in nitrogen-containing pollutant discharge in reducing regenerated flue gas,
Preferably, the catalyst is with (1:99)-(6:94) ratio is used in mixed way with industrial poising agent.
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|---|---|---|---|---|
| US20040167013A1 (en) * | 2003-02-20 | 2004-08-26 | Ou John D Y | Combined cracking and selective hydrogen combustion for catalytic cracking |
| CN1729041A (en) * | 2002-10-21 | 2006-02-01 | 格雷斯公司 | Reduction of gas phase reduced nitrogen species in partial burn FCC processes |
| CN102371150A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Composition for reducing discharge of NOx in regeneration flue gas of fluid catalytic cracking (FCC) |
| CN105126841A (en) * | 2015-07-29 | 2015-12-09 | 张冰童 | Composition for reducing discharge of oxygen-deficient regenerative flue gas HN3 and HCN and preparation method thereof |
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2017
- 2017-03-13 CN CN201710145467.9A patent/CN106807372B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1729041A (en) * | 2002-10-21 | 2006-02-01 | 格雷斯公司 | Reduction of gas phase reduced nitrogen species in partial burn FCC processes |
| US20040167013A1 (en) * | 2003-02-20 | 2004-08-26 | Ou John D Y | Combined cracking and selective hydrogen combustion for catalytic cracking |
| CN102371150A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Composition for reducing discharge of NOx in regeneration flue gas of fluid catalytic cracking (FCC) |
| CN105126841A (en) * | 2015-07-29 | 2015-12-09 | 张冰童 | Composition for reducing discharge of oxygen-deficient regenerative flue gas HN3 and HCN and preparation method thereof |
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