CN106925295B - It is a kind of reduce the pollutant emission of FCC regenerated flue gas co-catalyst and its application - Google Patents
It is a kind of reduce the pollutant emission of FCC regenerated flue gas co-catalyst and its application Download PDFInfo
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- CN106925295B CN106925295B CN201710145515.4A CN201710145515A CN106925295B CN 106925295 B CN106925295 B CN 106925295B CN 201710145515 A CN201710145515 A CN 201710145515A CN 106925295 B CN106925295 B CN 106925295B
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- 239000003426 co-catalyst Substances 0.000 title claims abstract description 77
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003546 flue gas Substances 0.000 title claims abstract description 48
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 12
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 306
- 239000004005 microsphere Substances 0.000 claims abstract description 276
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 24
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 36
- 238000005360 mashing Methods 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 238000007598 dipping method Methods 0.000 claims description 14
- 239000000809 air pollutant Substances 0.000 claims description 11
- 231100001243 air pollutant Toxicity 0.000 claims description 11
- 238000010009 beating Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000009938 salting Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910003978 SiClx Inorganic materials 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 4
- 238000005507 spraying Methods 0.000 claims 3
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 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
- 238000003756 stirring Methods 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 19
- 239000000395 magnesium oxide Substances 0.000 description 18
- 150000002823 nitrates Chemical class 0.000 description 18
- 230000000694 effects Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 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
- 230000032683 aging Effects 0.000 description 13
- 229910001593 boehmite Inorganic materials 0.000 description 13
- 239000000084 colloidal system Substances 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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 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
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 12
- 229920006395 saturated elastomer Polymers 0.000 description 12
- 238000012216 screening Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 10
- 239000000571 coke Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 9
- 239000012752 auxiliary agent Substances 0.000 description 8
- 239000011805 ball Substances 0.000 description 8
- 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 8
- 238000000034 method Methods 0.000 description 8
- 239000005995 Aluminium silicate Substances 0.000 description 7
- 235000012211 aluminium silicate Nutrition 0.000 description 7
- 235000018660 ammonium molybdate Nutrition 0.000 description 7
- 238000004523 catalytic cracking Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 6
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 6
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 6
- 229910003445 palladium oxide Inorganic materials 0.000 description 6
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 6
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229910001923 silver oxide Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910001930 tungsten oxide Inorganic materials 0.000 description 6
- 229910001935 vanadium oxide Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- OTCVAHKKMMUFAY-UHFFFAOYSA-N oxosilver Chemical class [Ag]=O OTCVAHKKMMUFAY-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002671 adjuvant Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 229910016287 MxOy Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- -1 nitrogenous compound Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 description 1
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910002676 Pd(NO3)2·2H2O Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 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
- 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
- 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
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen 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
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- 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
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of co-catalyst for reducing the pollutant emission of FCC regenerated flue gas and its applications.The co-catalyst includes microsphere particle A and microsphere particle B；It is in terms of 100% by the weight of microsphere particle A, the microsphere particle A includes: the aluminium oxide of 80-98%, the silica of 0.1-10%, the oxide of the rare earth element of the oxide and 0.1-3% selected from one or both of group vib and IB race metal of 1-15%；It is in terms of 100% by the weight of microsphere particle B, the microsphere particle B includes: the aluminium oxide of 50-80%, the oxide of the rare earth element of the oxide and 0.1-10% selected from one or more of Group IIA, Group IVB and VIII group metal of 10-50%.The co-catalyst is applied to reduce the discharge of nitrogen-containing pollutant, can substantially reduce the discharge of the atmosphere pollutions such as NOx, SOx and CO in regenerated flue gas.
Description
Technical field
The present invention relates to a kind of for reducing Air Pollutant Emissions such as NOx, SOx and CO in FCC apparatus regenerated flue gas
Co-catalyst and its application.
Background technique
Fluid catalytic cracking (hereinafter referred to as FCC) device is important one of the heavy oil lighting device of oil plant, is production
The important process of the Organic Chemicals such as the core apparatus of light oil especially high-knock rating gasoline, and production low-carbon alkene.
But containing a certain amount of SOx, NOx and CO etc. to the disagreeableness contaminant gases of environment in FCC regenerated flue gas.According to statistics, it refines
The 6%-7% and 10% of total release in SOx and NOx the difference duty gas of oily enterprise discharge, the overwhelming majority therein from
FCC apparatus.
NOx and SOx in FCC regenerated flue gas are mainly derived from nitrogenous compound and sulfur-containing compound in feedstock oil.?
In FCC riser reactor, while feedstock oil cracking, the small part coke laydown of generation makes its inactivation in catalyst surface,
Part sulphur and nitrogen enter coke, in a regenerator carry out catalyst coke burning regeneration process when, sulphur, nitrogen oxidation transformation at
SOx and NOx, is discharged into atmosphere with regenerated flue gas.There is correlative study to show (Jin S Yoo, John
A.Karch.Catalytic SOx abatement:The role of magnesium aluminate spinel in the
removal of SOx from fluid catalytic cracking(FCC)flue gas[J].Ind Eng Chem
Res, 1988,27:1356-1360), the sulfur content in catalytically cracked material is generally 0.3 weight %-3.0 weight %, in residual oil
Sulfur content is up to 4.0 weight %.After cracked, the about 35 weight %-45 weight % of sulphur in raw material is with H2The form of S enters gas
Product, 50 weight %-60 weight % enter liquid product, and 2 weight %-5 weight % enter coke, in a regenerator in coke
Sulphur is all oxidized to SOx.Nitrogen content in feedstock oil is generally very low, about 0.05 weight %-0.5 weight %.In cracking
In reaction process, basic nitrogen compound is adsorbed on the acid centre of catalyst and forms coke, and neutral nitrogen compound is then
It is considered entering in product, the nitrogen in raw material close to half enters coke.Nitrogen in catalyst regeneration burning process, on coke
Only 3%-25% enters flue gas in the form of NO, remaining is then converted into N2Form exist.NOx in FCC regenerated flue gas
Concentration is 0.005v%-0.05v%, mainly NO (about 90%), contains a small amount of NO simultaneously2；SOx is dense in FCC regenerated flue gas
Degree is 0.02v%-0.1v%, wherein about 90% is SO2, about 10% is SO3.It is same in FCC regenerated flue gas other than NOx and SOx
Shi Hanyou O2、CO2, CO and H2The concentration of O, these gases are influenced to change greatly by operating condition.
With the environmental regulation being increasingly stringenter both at home and abroad, to reduce atmosphere pollution, flue gas desulfurization, the denitration of FCC apparatus
And the thing that CO discharge is increasingly paid attention to as industry is reduced, FCC regenerated flue gas pollution reduction pressure is increasingly urgent.Many
It reduces in FCC regenerated flue gas in the technology of NOx, SOx and CO pollutant emission, is most to have using co-catalyst (abbreviation auxiliary agent)
Effect, most economical method.Therefore, a kind of multiple-effect co-catalyst is developed, it is dirty that NOx, SOx and CO in regenerated flue gas can be reduced simultaneously
Dye object discharge is research hotspot in recent years.Sanju Environment Protection New Material Co., Ltd., Beijing proposes the sulphur transfer combustion-supporting triple effect of denitrogenation
Agent and its preparation method and application (number of patent application CN02153284.2) simultaneously reports industrial application situation (catalytic cracking cigarette
Gas turns the industrial application of sulphur denitrogenation and combustion-supporting three functions catalyst FP-DSN, Chen Zhi etc., oil refining design, 2002,32 (11): 7-
11), which has the ability of SOx and NOx in stronger removing flue gas, while having CO combustion-supporting effect.When application test, then
The average removal efficiency of SOx is up to 72.85% (SOx initial concentration 736mg/m in raw device flue gas3), the average removal efficiency of NOx reaches
85.90% (NOx initial concentration 269mg/m3)；In addition, Tianjin Tuo get petroleum technology Development Co., Ltd also has developed a kind of cigarette
Desulfurization, denitration, combustion-supporting triple effect auxiliary agent have simultaneously carried out industrial application (triple effect auxiliary agent answering in catalytic cracking unit flue gas desulfurization
With Zhou Jianwen etc. refines oil engineering and technology, 2015,45 (3): 43-45；The combustion-supporting triple effect auxiliary agent of sulfur transfer additive coordinated desulfurization denitration
Application on catalytic cracking unit, white clouds wave etc., Speciality Petrochemicals, 2016,33 (1): 50-55).Triple effect auxiliary agent accounts for system
When about 2.90 weight % of total catalyst reserve, flue gas desulphuization rate is 76.98% (SOx initial concentration 821.7-983.3mg/m3),
Significant desulfurization effect；Flue-gas denitrification rate is 61.11% (NOx initial concentration 99.0-119.0mg/m3)；Triple effect auxiliary agent is combustion-supporting simultaneously
It works well, alternative CO combustion adjuvant.Currently, the development and application of triple effect co-catalyst reduce FCC dress to a certain extent
The discharge of flue gas pollutant is set, but totally apparently, the mainly de- SOx of triple effect co-catalyst in industrial application report is used
Occasion is mostly the device not high in NOx initial concentration, and the use of these co-catalysts has not been reached yet under the conditions of high concentrate NOx
The target of efficient removal SOx.
Research finds dense-phase bed exit CO, CO2、O2Content be respectively 1.7%, 14.2%, 1.9%；And regenerator
CO, CO in the flue gas of outlet2、O2Content be respectively 0.1%, 16.3%, 1.0%, even if this explanation is the completely burned the case where
Under, regenerator dense-phase bed still has the carbon monoxide of high level, and the oxidation of CO occurs mainly in dilute phase bed.This is because
The uneven distribution of gas and combustion adjuvant in fluidized bed causes oxygen transmitting uneven, dense-phase bed O2Content is low, CO content compared with
High (catalytic cracking process and engineering, Chen Junwu etc., Sinopec publishing house, 1995, P944).
Summary of the invention
In order to solve the above technical problems, the object of the present invention is to provide a kind of reduction FCC regenerated flue gas pollutant emissions
Co-catalyst and its application, to achieve the purpose that substantially reduce the Air Pollutant Emissions such as NOx, SOx and CO in regenerated flue gas.
In order to achieve the above object, the present invention provides it is a kind of reduce the pollutant emission of FCC regenerated flue gas co-catalyst,
The co-catalyst includes microsphere particle A and microsphere particle B；
It is in terms of 100% by the weight of microsphere particle A, microsphere particle A includes: the aluminium oxide of 80-98%, the oxygen of 0.1-10%
SiClx, the oxygen of the rare earth element of the oxide and 0.1-3% selected from one or both of group vib and IB race metal of 1-15%
Compound；
It is in terms of 100% by the weight of microsphere particle B, microsphere particle B includes: the aluminium oxide of 50-80%, the choosing of 10-50%
From the oxide of the rare earth element of the oxide and 0.1-10% of one or more of Group IIA, Group IVB and VIII group metal.
In above-mentioned co-catalyst, it is preferable that the weight ratio of microsphere particle A and microsphere particle B are (1:3)-(3:1).
In above-mentioned co-catalyst, it is preferable that the heap density of microsphere particle A is 0.85-1.00g/mL, microsphere particle B's
Heap density is 0.75-0.85g/mL.
In above-mentioned co-catalyst, it is preferable that the sieve of microsphere particle A is grouped into 0-20 μm < 0.1 weight %, microballoon
The sieve of grain B is grouped into 0-20 μm < 4.0 weight %.
In above-mentioned co-catalyst, it is preferable that in microsphere particle A:
The combination that metal in group vib is one or both of Mo and W, the weight percent of oxide are no more than micro-
The 10% of ball particle A；
Metal in IB race is Ag, and the weight percent of oxide is no more than the 3% of microsphere particle A；
Rare earth element is Ce, and the weight percent of oxide accounts for the 0.2-2% of microsphere particle A.
In above-mentioned co-catalyst, it is preferable that in microsphere particle B:
The metal of Group IIA is Mg, and the weight percent of oxide is no more than the 50% of microsphere particle B；
The metal of Group IVB is V, and the weight percent of oxide is no more than the 5% of microsphere particle B；
The metal of VIII group is Fe and Pd, and the weight percent of oxide is no more than the 4% of microsphere particle B；
Rare earth element is Ce, and the weight percent of oxide is no more than the 6% of microsphere particle A.
Specific embodiment according to the present invention, it is preferable that microsphere particle A is prepared by the following steps to obtain: will contain
There is the silicon source of aluminium oxide to be beaten, control slurries pH, be then mixed with beating with the silicon source containing silica, then be spray-dried, roast,
Microsphere particle carrier is obtained, microsphere particle carrier is used into the salting liquid for being selected from one or both of VB race, IB race metal and is contained
There is the salt solution impregnation of rare earth element, microsphere particle A is obtained after drying, roasting；
Wherein, microsphere particle B is prepared by the following steps to obtain: the silicon source containing aluminium oxide is subjected to mashing plastic,
Slurries pH is controlled, the oxide selected from one or more of Group IIA, Group IVB and VIII group metal is then added, mixing is beaten
Slurry, then be spray-dried, roast, microsphere particle carrier is obtained, by microsphere particle carrier in Group IIA, Group IVB and VIII group
One or more of metals salting liquid and containing rare earth element metal salt solution dipping, obtain microballoon after drying, roasting
Particle B.
In the preparation process of above-mentioned co-catalyst, it is preferable that when being mixed with beating, adjust the component containing silica
Additional amount makes the heap density 0.85-1.00g/mL of microsphere particle A；In the same manner, when being mixed with beating, adjusting contains Group IIA
The additional amount of oxide makes the heap density 0.75-0.85g/mL of microsphere particle B.
In the preparation process of above-mentioned co-catalyst, it is preferable that control slurries pH is 1.2-2.0；Dry temperature is
120-280 DEG C, the dry time is 1-3 hours；It is highly preferred that dry temperature is 180-200 DEG C, the dry time is 1-2
Hour；
The temperature of roasting is 500-800 DEG C, time 1-4 hour of roasting；It is highly preferred that 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 processing technology, without particular/special requirement.
Above-mentioned co-catalyst can be applied to reduce the discharge of nitrogen-containing pollutant, it is preferable that the present invention is according to regenerated flue gas
Middle NOxMicrosphere particle A and microsphere particle B is carried out mixing as co-catalysis according to same ratio (weight ratio) by the volume ratio of/SOx
Agent uses, which is used in mixed way with the ratio of (1:99)-(6:94) and industrial poising agent.
The characteristics of present invention coexists according to NOx in regenerator dense-phase bed and CO, makees NOx reducing agent with CO, provides one kind
Heap density is slightly larger than the microsphere particle A of FCC catalyst, is distributed in fluidized bed dense-phase bed probability using the big microsphere particle of heap density
Big characteristic selects suitable active component to make it in dense-phase bed to reaction NO+CO → N2+CO2Have high catalytic activity and
Selectivity, at the same in view of in dense-phase bed coke the burning of institute's sulfur-containing compound generate SOx, SOx easily makes catalyst poisoning, so
The ability that there is the microsphere particle A of offer sulfur resistive oxide to poison；And a kind of heap density is provided and is slightly less than the micro- of FCC catalyst
Ball particle B selects suitable active group using the heap density minimicrosphere distribution of particles characteristic big in fluidized bed dilute phase bed probability
Dividing makes it in dilute phase bed to reaction CO+O2→CO2、SO2+O2→SO3And MxOy+SO3→Mx(SO4)Z(SO3In microsphere particle B
Upper react with active component MxOy generates sulfate Mx (SO4) z) there are high catalytic activity and selectivity, and on microsphere particle B
The sulfate of formation is easy to happen M in riser reactorx(SO4)Z+H2(C3H8)→MxOyReaction and realize reduction.And
To two kinds of microsphere particles A and B of offer, according to the content of NOx, SOx and CO pollutant in regenerated flue gas according to different ratios
Be mixed to form co-catalyst, in FCC regenerator using can strengthen respectively removing NOx, SOx that dilute, dense-phase bed occurs and
The reaction of CO significantly reduces the discharge of the atmosphere pollutions such as NOx, SOx and CO in regenerated flue gas.
It can be by the NOx in regenerated flue gas from 500mg/m using above-mentioned co-catalyst in FCC apparatus3It is reduced to 95mg/m3,
Removal efficiency reaches 81%；SO in flue gasXFrom 685mg/m3It is reduced to 101mg/m3, removal efficiency reaches 85.3%；CO in flue gas
Content reduces 9.3% compared with using Pt combustion adjuvant；And no negative shadow is received in the addition of co-catalyst to FCC total liquid yield and gently
It rings, the yield of main purpose product is basically unchanged.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
The raw materials used metal salt for market sale in each embodiment, such as cobalt nitrate (Co (NO3)2·6H2It O) is Tianjin
The production of development in science and technology Co., Ltd is recovered in city；Silver nitrate (AgNO3) it is that Zhengzhou Hua Mao chemical products Co., Ltd produces；Palladium nitrate
(Pd(NO3)2·2H2O) production of fine chemistry industry research institute is recovered for Tianjin；Cerous nitrate (Ce (NO3)3·6H2O) auspicious rich for Zibo
The production of health rare earth material Co., Ltd；Ferric nitrate (Fe (NO3)3·9H2It O is) the prosperous beautiful peaking plant produced in Taiyuan City；Or market pin
Sell the solvable metallic salt with water and heat resolve as oxide, such as ammonium metavanadate (NH4VO3) it is to analyze pure, Tianjin light
Multiple development in science and technology Co., Ltd production, ammonium metatungstate ((NH4)6W7O24·6H2O) pure to analyze, Chinese medicines group chemical reagent is limited
Company's production；Ammonium molybdate ((NH4)6Mo7O24·4(H2O)) pure to analyze, Shanghai Aladdin biochemical technology limited liability company is raw
It produces；The boehmite (wherein 60 weight % of alumina content) of Shandong Aluminium Industrial Corp's production；Kaolin is Suzhou China kaolinite
God in charge of the Earth department produces (SiO256 weight % of content), hydrochloric acid (36.5 weight % of concentration, chemistry are pure) used, Beijing Chemical Plant's production；
Magnesia (MgO) is that Weifang Xu Hui new material Co., Ltd produces (98 weight % of > content).
Embodiment 1
Present embodiments provide a kind of co-catalysis for reducing the Air Pollutant Emissions such as NOx, SOx and CO in regenerated flue gas
Agent, the co-catalyst include microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by the following steps to obtain:
Deionized water is added in a stirring kettle, 1.576 kilograms of boehmite mashing are then added, control slurry solid content
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, controls slurries pH=1.2-2.0, is beaten about 60 minutes；Continue
0.097 kilogram of kaolin is added in stirred tank, is beaten about 60 minutes；It is heated to 60-80 DEG C, stands 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 roasted 120 minutes at 700 DEG C, obtains 1 kilogram of microsphere particle carrier.The microsphere particle carrier is salic
94.57 weight %, 5.43 weight % of silica.
On the basis of 1 kilogram of microsphere particle carrier (butt), by 63.4 grams of ammonium metatungstates, 13.4 grams of ammonium molybdates, 16 grams
Silver nitrate, 27.6 grams of cerous nitrates are configured to solution respectively, stir evenly.Dipping microsphere particle carrier is saturated with solution, then 180
DEG C drying 120 minutes, in 700 DEG C roast 120 minutes, obtain microsphere particle A.
Microsphere particle A is sieved, forms the screening of microsphere particle A are as follows: 0-20 μm of particle < 0.1 weight %.Finally, micro-
The heap density of ball particle A is 0.9g/mL, the composition of microsphere particle A containing 87.0 weight % aluminium oxide, 5.0 weight % silica,
5.0 weight % tungsten oxides, 1.0 weight % molybdenum oxides, 1.0 weight % silver oxides, 1.0 weight % cerium oxide.
Wherein, microsphere particle B is prepared by the following steps to obtain:
Deionized water is added in a stirring kettle, 1.491 kilograms of boehmite mashing are then added, control slurry solid content
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, controls slurries pH=1.2-2.0, is beaten about 60 minutes；Continue
0.107 kilogram of magnesia is added in stirred tank, is beaten about 60 minutes；It is heated to 70-90 DEG C, stands 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 roasted 120 minutes at 600 DEG C, obtains 1 kilogram of microsphere particle carrier.Microsphere particle carrier composition is oxygen-containing
Change 89.45 weight % of aluminium, 10.55 weight % of magnesia.
On the basis of 1 kilogram of microsphere particle carrier (butt), by 2.7 grams of ammonium metavanadates, 107.3 grams of ferric nitrates, 0.9 gram
Palladium nitrate, 80.2 grams of cerous nitrates are configured to solution respectively, stir evenly.Dipping microsphere particle carrier is saturated with solution, then 180
DEG C drying 120 minutes, in 700 DEG C roast 120 minutes, obtain microsphere particle B.
Microsphere particle B is sieved, forms the screening of microsphere particle B are as follows: 0-20 μm of particle < 4 weight %.Finally, microballoon
The heap density of particle B is 0.8g/mL, the composition of microsphere particle B containing 84.76 weight % aluminium oxide, 10.0 weight % magnesia,
0.2 weight % vanadium oxide, 2.0 weight % iron oxide, 0.04 weight % of palladium oxide, 3.0 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B are 1:1 in the co-catalyst.
Embodiment 2
Present embodiments provide a kind of co-catalysis for reducing the Air Pollutant Emissions such as NOx, SOx and CO in regenerated flue gas
Agent, the co-catalyst include microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by the following steps to obtain:
Deionized water is added in a stirring kettle, 1.665 kilograms of boehmite mashing are then added, control slurry solid content
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, controls slurries pH=1.2-2.0, is beaten about 60 minutes；Continue
0.002 kilogram of kaolin is added in stirred tank, is beaten about 60 minutes；It is heated to 60-80 DEG C, stands 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 roasted 120 minutes at 700 DEG C, obtains 1 kilogram of microsphere particle carrier.The microsphere particle carrier is salic
99.90 weight %, 0.1 weight % of silica.
On the basis of 1 kilogram of microsphere particle carrier (butt), by 24 grams of ammonium metatungstates, 6.3 grams of ammonium molybdates, 1.5 grams of nitre
Sour silver, 5.2 grams of cerous nitrates are configured to solution respectively, stir evenly.It is saturated with solution and impregnates microsphere particle carrier, then 180 DEG C
Drying 120 minutes roasts 120 minutes in 700 DEG C, obtains microsphere particle A.
Microsphere particle A is sieved, forms the screening of microsphere particle A are as follows: 0-20 μm of particle < 0.1 weight %.Finally, micro-
The heap density of ball particle A is 0.9g/mL, the composition of microsphere particle A containing 97.1 weight % aluminium oxide, 0.1 weight % silica,
2.0 weight % tungsten oxides, 0.5 weight % molybdenum oxide, 0.1 weight % silver oxide, 0.2 weight % cerium oxide.
Wherein, microsphere particle B is prepared by the following steps to obtain:
Deionized water is added in a stirring kettle, 0.883 kilogram of boehmite mashing is then added, controls slurry solid content
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, controls slurries pH=1.2-2.0, is beaten about 60 minutes；Continue
0.48 kilogram of magnesia is added in stirred tank, is beaten about 60 minutes；It is heated to 70-90 DEG C, stands aging about 120 minutes simultaneously
Continue stirring 30 minutes, then by the colloid material after mashing with spray drying system is pumped into, obtains microsphere particle carrier, it will
Microsphere particle carrier roasts 120 minutes at 600 DEG C, obtains 1 kilogram of microsphere particle carrier.The microsphere particle carrier forms oxygen-containingization
52.97 weight % of aluminium, 47.03 weight % of magnesia.
On the basis of 1 kilogram of microsphere particle carrier (butt), by 53.9 grams of ammonium metavanadates, 5.3 grams of ferric nitrates, 0.5 gram
Palladium nitrate, 5.3 grams of cerous nitrates are configured to solution respectively, stir evenly.Dipping microsphere particle carrier is saturated with solution, then 180
DEG C drying 120 minutes, in 700 DEG C roast 120 minutes, obtain microsphere particle B.
Microsphere particle B is sieved, forms the screening of microsphere particle B are as follows: 0-20 μm of particle < 4 weight %.Finally, microballoon
The heap density of particle B is 0.8g/mL, the composition of microsphere particle B containing 50.68 weight % aluminium oxide, 45.0 weight % magnesia,
4.0 weight % vanadium oxides, 0.1 weight % iron oxide, 0.02 weight % of palladium oxide, 0.2 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B are 1:1 in the co-catalyst.
Embodiment 3
Present embodiments provide a kind of co-catalysis for reducing the Air Pollutant Emissions such as NOx, SOx and CO in regenerated flue gas
Agent, the co-catalyst include microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by the following steps to obtain:
Deionized water is added in a stirring kettle, 1.468 kilograms of boehmite mashing are then added, control slurry solid content
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, controls slurries pH=1.2-2.0, is beaten about 60 minutes；Continue
0.213 kilogram of kaolin is added in stirred tank, is beaten about 60 minutes；It is heated to 60-80 DEG C, stands 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 roasted 120 minutes at 700 DEG C, obtains 1 kilogram of microsphere particle carrier.The microsphere particle carrier is salic
88.10 weight %, 11.90 weight % of silica.
On the basis of 1 kilogram of microsphere particle carrier (butt), by 125 grams of ammonium metatungstates, 43.9 ammonium molybdates, 35.1 grams of nitre
Sour silver, 60.4 grams of cerous nitrates are configured to solution respectively, stir evenly.It is saturated with solution and impregnates microsphere particle carrier, then 180 DEG C
Drying 120 minutes roasts 120 minutes in 700 DEG C, obtains microsphere particle A.
Microsphere particle A is sieved, forms the screening of microsphere particle A are as follows: 0-20 μm of particle < 0.1 weight %.Finally, micro-
The heap density of ball particle A is 0.9g/mL, the composition of microsphere particle A containing 74.0 weight % aluminium oxide, 10.0 weight % silica,
9.0 weight % tungsten oxides, 3.0 weight % molybdenum oxides, 2.0 weight % silver oxides, 2.0 weight % cerium oxide.
Wherein, microsphere particle B is prepared by the following steps to obtain:
Deionized water is added in a stirring kettle, 1.104 kilograms of boehmite mashing are then added, control slurry solid content
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, controls slurries pH=1.2-2.0, is beaten about 60 minutes；Continue
0.344 kilogram of magnesia is added in stirred tank to be beaten about 60 minutes；Mashing about 60 minutes；It is heated to 70-90 DEG C, is stood old
Change about 120 minutes and continue stirring 30 minutes, then by the colloid material after mashing be pumped into spray drying system obtain it is micro-
Ball particle carrier, microsphere particle carrier is roasted at 600 DEG C and obtains within 120 minutes 1 kilogram of microsphere particle carrier, which carries
Body forms salic 66.27 weight %, 33.73 weight % of magnesia.
On the basis of 1 kilogram of microsphere particle carrier (butt), by 29 grams of ammonium metavanadates, 17.2 ferric nitrates, 1.5 grams of nitric acid
Palladium, 17.1 grams of cerous nitrates are configured to solution respectively, stir evenly.It is saturated dipping microsphere particle carrier with solution, then 180 DEG C of bakings
It is 120 minutes dry, it is roasted 120 minutes in 700 DEG C, obtains microsphere particle B.
Microsphere particle B is sieved, the screening of microsphere particle B is made to form 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 58.94 weight % aluminium oxide, 30.0 weight % magnesia, 2.0 weights
Measure % vanadium oxide, 3.0 weight % iron oxide, 0.06 weight % of palladium oxide, 6.0 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B are 1:1 in the co-catalyst.
Embodiment 4
Present embodiments provide a kind of co-catalysis for reducing the Air Pollutant Emissions such as NOx, SOx and CO in regenerated flue gas
Agent, the co-catalyst include microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by the following steps to obtain:
Deionized water is added in a stirring kettle, 1.468 kilograms of boehmite mashing are then added, control slurry solid content
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, controls slurries pH=1.2-2.0, is beaten about 60 minutes；Continue
0.213 kilogram of kaolin is added in stirred tank, is beaten about 60 minutes；It is heated to 60-80 DEG C, stands 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 roasted 120 minutes at 700 DEG C, obtains 1 kilogram of microsphere particle carrier.The microsphere particle carrier is salic
88.10 weight %, 11.90 weight % of silica.
On the basis of 1 kilogram of microsphere particle carrier (butt), by 125 grams of ammonium metatungstates, 43.9 ammonium molybdates, 35.1 grams of nitre
Sour silver, 60.4 grams of cerous nitrates are configured to solution respectively, stir evenly.It is saturated with solution and impregnates microsphere particle carrier, then 180 DEG C
Drying 120 minutes roasts 120 minutes in 700 DEG C, obtains microsphere particle A.
Microsphere particle A is sieved, forms the screening of microsphere particle A are as follows: 0-20 μm of particle < 0.1 weight %.Finally, micro-
The heap density of ball particle A is 0.9g/mL, the composition of microsphere particle A containing 74.0 weight % aluminium oxide, 10.0 weight % silica,
9.0 weight % tungsten oxides, 3.0 weight % molybdenum oxides, 2.0 weight % silver oxides, 2.0 weight % cerium oxide.
Wherein, microsphere particle B is prepared by the following steps to obtain:
Deionized water is added in a stirring kettle, 1.491 kilograms of boehmite mashing are then added, control slurry solid content
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, controls slurries pH=1.2-2.0, is beaten about 60 minutes；Continue
0.107 kilogram of magnesia is added in stirred tank, is beaten about 60 minutes；It is heated to 70-90 DEG C, stands 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 roasted 120 minutes at 600 DEG C, obtains 1 kilogram of microsphere particle carrier.Microsphere particle carrier composition is oxygen-containing
Change 89.45 weight % of aluminium, 10.55 weight % of magnesia.
On the basis of 1 kilogram of microsphere particle carrier (butt), by 2.7 grams of ammonium metavanadates, 107.3 grams of ferric nitrates, 0.9 gram
Palladium nitrate, 80.2 grams of cerous nitrates are configured to solution respectively, stir evenly.Dipping microsphere particle carrier is saturated with solution, then 180
DEG C drying 120 minutes, in 700 DEG C roast 120 minutes, obtain microsphere particle B.
Microsphere particle B is sieved, forms the screening of microsphere particle B are as follows: 0-20 μm of particle < 4 weight %.Finally, microballoon
The heap density of particle B is 0.8g/mL, the composition of microsphere particle B containing 84.76 weight % aluminium oxide, 10.0 weight % magnesia,
0.2 weight % vanadium oxide, 2.0 weight % iron oxide, 0.04 weight % of palladium oxide, 3.0 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B are 1:1.37 in the co-catalyst.
Embodiment 5
Present embodiments provide a kind of co-catalysis for reducing the Air Pollutant Emissions such as NOx, SOx and CO in regenerated flue gas
Agent, the co-catalyst include microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by the following steps to obtain:
Deionized water is added in a stirring kettle, 1.468 kilograms of boehmite mashing are then added, control slurry solid content
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, controls slurries pH=1.2-2.0, is beaten about 60 minutes；Continue
0.213 kilogram of kaolin is added in stirred tank, is beaten about 60 minutes；It is heated to 60-80 DEG C, stands 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 roasted 120 minutes at 700 DEG C, obtains 1 kilogram of microsphere particle carrier.The microsphere particle carrier is salic
88.10 weight %, 11.90 weight % of silica.
On the basis of 1 kilogram of microsphere particle carrier (butt), by 125 grams of ammonium metatungstates, 43.9 ammonium molybdates, 35.1 grams of nitre
Sour silver, 60.4 grams of cerous nitrates are configured to solution respectively, stir evenly.It is saturated with solution and impregnates microsphere particle carrier, then 180 DEG C
Drying 120 minutes roasts 120 minutes in 700 DEG C, obtains microsphere particle A.
Microsphere particle A is sieved, forms the screening of microsphere particle A are as follows: 0-20 μm of particle < 0.1 weight %.Finally, micro-
The heap density of ball particle A is 0.9g/mL, and the composition of microsphere particle A contains 74.0 weight % aluminium oxide, 10.0 weight % silica,
9.0 weight % tungsten oxides, 3.0 weight % molybdenum oxides, 2.0 weight % silver oxides, 2.0 weight % cerium oxide.
Wherein, microsphere particle B is prepared by the following steps to obtain:
Deionized water is added in a stirring kettle, 0.883 kilogram of boehmite mashing is then added, controls slurry solid content
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, controls slurries pH=1.2-2.0, is beaten about 60 minutes；Continue
0.48 kilogram of magnesia is added in stirred tank, is beaten about 60 minutes；It is heated to 70-90 DEG C, stands aging about 120 minutes simultaneously
Continue stirring 30 minutes, then by the colloid material after mashing with spray drying system is pumped into, obtains microsphere particle carrier, it will
Microsphere particle carrier roasts 120 minutes at 600 DEG C, obtains 1 kilogram of microsphere particle carrier.The microsphere particle carrier forms oxygen-containingization
52.97 weight % of aluminium, 47.03 weight % of magnesia.
On the basis of 1 kilogram of microsphere particle carrier (butt), by 53.9 grams of ammonium metavanadates, 5.3 grams of ferric nitrates, 0.5 gram
Palladium nitrate, 5.3 grams of cerous nitrates are configured to solution respectively, stir evenly.Dipping microsphere particle carrier is saturated with solution, then 180
DEG C drying 120 minutes, in 700 DEG C roast 120 minutes, obtain microsphere particle B.
Microsphere particle B is sieved, forms the screening of microsphere particle B are as follows: 0-20 μm of particle < 4 weight %.Finally, microballoon
The heap density of particle B is 0.8g/mL, the composition of microsphere particle B containing 50.68 weight % aluminium oxide, 45.0 weight % magnesia,
4.0 weight % vanadium oxides, 0.1 weight % iron oxide, 0.02 weight % of palladium oxide, 0.2 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B are 1:1.37 in the co-catalyst.
Embodiment 6
Present embodiments provide a kind of co-catalysis for reducing the Air Pollutant Emissions such as NOx, SOx and CO in regenerated flue gas
Agent, the co-catalyst include microsphere particle A and microsphere particle B.
Wherein, microsphere particle A is prepared by the following steps to obtain:
Deionized water is added in a stirring kettle, 1.576 kilograms of boehmite mashing are then added, control slurry solid content
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, controls slurries pH=1.2-2.0, is beaten about 60 minutes；Continue
0.097 kilogram of kaolin is added in stirred tank, is beaten about 60 minutes；It is heated to 60-80 DEG C, stands 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 roasted 120 minutes at 700 DEG C, obtains 1 kilogram of microsphere particle carrier.The microsphere particle carrier is salic
94.57 weight %, 5.43 weight % of silica.
On the basis of 1 kilogram of microsphere particle carrier (butt), by 63.4 grams of ammonium metatungstates, 13.4 grams of ammonium molybdates, 16 grams
Silver nitrate, 27.6 grams of cerous nitrates are configured to solution respectively, stir evenly.Dipping microsphere particle carrier is saturated with solution, then 180
DEG C drying 120 minutes, in 700 DEG C roast 120 minutes, obtain microsphere particle A.
Microsphere particle A is sieved, forms the screening of microsphere particle A are as follows: 0-20 μm of particle < 0.1 weight %.Finally, micro-
The heap density of ball particle A is 0.9g/mL, the composition of microsphere particle A containing 87.0 weight % aluminium oxide, 5.0 weight % silica,
5.0 weight % tungsten oxides, 1.0 weight % molybdenum oxides, 1.0 weight % silver oxides, 1.0 weight % cerium oxide.
Wherein, microsphere particle B is prepared by the following steps to obtain:
Deionized water is added in a stirring kettle, 0.883 kilogram of boehmite mashing is then added, controls slurry solid content
It is 12% or so, is beaten about 30 minutes；Hydrochloric acid solution is added, controls slurries pH=1.2-2.0, is beaten about 60 minutes；Continue
0.48 kilogram of magnesia is added in stirred tank, is beaten about 60 minutes；It is heated to 70-90 DEG C, stands aging about 120 minutes simultaneously
Continue stirring 30 minutes, then by the colloid material after mashing with spray drying system is pumped into, obtains microsphere particle carrier, it will
Microsphere particle carrier roasts 120 minutes at 600 DEG C, obtains 1 kilogram of microsphere particle carrier.The microsphere particle carrier forms oxygen-containingization
52.97 weight % of aluminium, 47.03 weight % of magnesia.
On the basis of 1 kilogram of microsphere particle carrier (butt), by 53.9 grams of ammonium metavanadates, 5.3 grams of ferric nitrates, 0.5 gram
Palladium nitrate, 5.3 grams of cerous nitrates are configured to solution respectively, stir evenly.Dipping microsphere particle carrier is saturated with solution, then 180
DEG C drying 120 minutes, in 700 DEG C roast 120 minutes, obtain microsphere particle B.
Microsphere particle B is sieved, forms the screening of microsphere particle B are as follows: 0-20 μm of particle < 4 weight %.Finally, microballoon
The heap density of particle B is 0.8g/mL, the composition of microsphere particle B containing 50.68 weight % aluminium oxide, 45.0 weight % magnesia,
4.0 weight % vanadium oxides, 0.1 weight % iron oxide, 0.02 weight % of palladium oxide, 0.2 weight % cerium oxide.
The weight ratio of microsphere particle A and microsphere particle B are 1:1.37 in the co-catalyst.
Embodiment 7
Present embodiments provide a kind of co-catalysis for reducing the Air Pollutant Emissions such as NOx, SOx and CO in regenerated flue gas
Agent, the co-catalyst only include microsphere particle A.The preparation method of microsphere particle A is shown in embodiment 4.
Embodiment 8
Present embodiments provide a kind of co-catalysis for reducing the Air Pollutant Emissions such as NOx, SOx and CO in regenerated flue gas
Agent, the co-catalyst only include microsphere particle B.The preparation method of microsphere particle B is shown in embodiment 4.
Comparative example 1
The co-catalyst that comparative example 1 selects is the commodity for having been used to industrial application in the prior art: CO combustion adjuvant (Shandong
Jun Fei Chemical Co., Ltd.).
Comparative example 2
The co-catalyst that comparative example 2 selects is the commodity for having been used to industrial application in the prior art: TUD-DNS3 auxiliary agent
(Tianjin Tuo get petroleum technology Development Co., Ltd).
Comparative example 3
The co-catalyst that comparative example 3 selects is the commodity for having been used to industrial application in the prior art: FP-DSN auxiliary agent (north
Capital trimerization environmental friendly material limited liability company).
Experimental performance evaluation result
The chemical composition of co-catalyst in each embodiment and comparative example is by x-ray fluorescence spectrometry.
With German MRU company E8500 Portable smoke analysis instrument analysis flue gas composition, including O2, NO, NOx, SOx, CO and
CO2Content.
It is needed for the co-catalyst of performance evaluation in advance in fluidized bed hydrothermal aging device in each embodiment and comparative example
800 DEG C, 100% vapor aging 10 hours are carried out, then (middle Effect of Catalysis In Petrochemistry agent Chang Ling branch company is raw with FCC industry poising agent
The CDC catalytic cracking catalyst of production) mixing, co-catalyst and FCC industry poising agent weight ratio are 3:97, successive reaction-again
It is evaluated on the raw medium-sized experimental provision of catalytic cracking, 10 kilograms of co-catalyst loading amount, 500 DEG C of reaction temperature, co-catalyst is again
Raw 700 DEG C of temperature.
1, the raw material oil nature that the present invention uses is as shown in table 1.
Table 1
| Project | Data | Project | Data |
| Elemental analysis, m% | Density (20 DEG C), g/cm3 | 0.921 | |
| C | 86.77 | Carbon residue, m% | 4.51 |
| H | 12.64 | Race's composition, m% | |
| S | 0.24 | Saturation point | 42.1 |
| N | 0.15 | Aromatic hydrocarbons point | 33.6 |
| Tenor, ug/g | Colloid | 24.1 | |
| Fe | 5.94 | Asphalitine | 0.2 |
| Ni | 11.60 | ||
| V | 4.15 | ||
| Na | 0.50 |
Material density 0.921g/cm3, it is to refine at present that carbon residue 4.51wt%, S, N element composition, which are in higher level,
The typical case that factory uses urges raw material again.NOx, SOx and CO content are higher in flue gas when catalyst regeneration process.2, co-catalyst and change
It is as shown in table 2 to learn composition.
Table 2
3, the co-catalyst in Application Example and comparative example, the concentration and variation of major pollutants in regenerated flue gas, such as
Shown in table 3.
Embodiment 1-6 plays a role to NOx, SOx and CO in flue gas is reduced, and wherein embodiment 4 and blank assay compare
Example 1 compares, and NOx, SOx and CO in flue gas reduce 81.0%, 85.3% and 9.3% respectively, shows good de-
Except effect.In embodiment 7 and 8, A particle or B particle is used alone, removing NOx, SOx and and CO in terms of have one respectively
Fixed limitation does not play optimal effect.
Table 3
4, the co-catalyst in embodiment and comparative example is as shown in table 4 to the performance of catalytic cracking product.
Table 4
The addition of institute's cocatalyst has little effect product distribution, and wherein the dry gas and coke of embodiment 3,4 produce
Rate is slightly lower, is better than other co-catalysts.
Claims (25)
1. it is a kind of reduce FCC regenerated flue gas in nitrogen-containing pollutant discharge co-catalyst, the co-catalyst include microsphere particle A and
Microsphere particle B；
It is in terms of 100% by the weight of microsphere particle A, the microsphere particle A includes: the aluminium oxide of 80-98%, the oxygen of 0.1-10%
SiClx, the oxygen of the rare earth element of the oxide and 0.1-3% selected from one or both of group vib and IB race metal of 1-15%
Compound；
It is in terms of 100% by the weight of microsphere particle B, the microsphere particle B includes: the aluminium oxide of 50-80%, the choosing of 10-50%
From the oxide of the rare earth element of the oxide and 0.1-10% of one or more of Group IIA, Group IVB and VIII group metal.
2. co-catalyst as described in claim 1, wherein the weight ratio of the microsphere particle A and microsphere particle B is (1:3)-
(3:1)。
3. co-catalyst as described in claim 1, 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. co-catalyst as claimed in claim 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.
5. such as co-catalyst of any of claims 1-4, wherein the sieve of the microsphere particle A is grouped into 0-20 μ
The weight of m < 0.1 %, the sieve of the microsphere particle B are grouped into 0-20 μm < 4.0 weight %.
6. such as co-catalyst of any of claims 1-4, wherein in microsphere particle A:
The weight percent of the combination that metal in the group vib is one or both of Mo and W, oxide is no more than institute
State the 10% of microsphere particle A；
Metal in the IB race is Ag, and the weight percent of oxide is no more than the 3% of the microsphere particle A；
The rare earth element is Ce, and the weight percent of oxide accounts for the 0.2-2% of the microsphere particle A.
7. co-catalyst as claimed in claim 5, wherein in microsphere particle A:
The weight percent of the combination that metal in the group vib is one or both of Mo and W, oxide is no more than institute
State the 10% of microsphere particle A；
Metal in the IB race is Ag, and the weight percent of oxide is no more than the 3% of the microsphere particle A；
The rare earth element is Ce, and the weight percent of oxide accounts for the 0.2-2% of the microsphere particle A.
8. the co-catalyst as described in any one of claim 1-4,7, wherein in microsphere particle B:
The metal of the Group IIA is Mg, and the weight percent of oxide is no more than the 50% of the microsphere particle B；
The metal of the Group IVB is V, and the weight percent of oxide is no more than the 5% of the microsphere particle B；
The metal of the VIII group is Fe and Pd, and the weight percent of oxide is no more than the 4% of the microsphere particle B；
The rare earth element is Ce, and the weight percent of oxide is no more than the 6% of the microsphere particle A.
9. co-catalyst as claimed in claim 5, wherein in microsphere particle B:
The metal of the Group IIA is Mg, and the weight percent of oxide is no more than the 50% of the microsphere particle B；
The metal of the Group IVB is V, and the weight percent of oxide is no more than the 5% of the microsphere particle B；
The metal of the VIII group is Fe and Pd, and the weight percent of oxide is no more than the 4% of the microsphere particle B；
The rare earth element is Ce, and the weight percent of oxide is no more than the 6% of the microsphere particle A.
10. co-catalyst as claimed in claim 6, wherein in microsphere particle B:
The metal of the Group IIA is Mg, and the weight percent of oxide is no more than the 50% of the microsphere particle B；
The metal of the Group IVB is V, and the weight percent of oxide is no more than the 5% of the microsphere particle B；
The metal of the VIII group is Fe and Pd, and the weight percent of oxide is no more than the 4% of the microsphere particle B；
The rare earth element is Ce, and the weight percent of oxide is no more than the 6% of the microsphere particle A.
11. the co-catalyst as described in any one of claim 1-4,7,9-10, wherein the microsphere particle A is by following
What step was prepared: will containing the aluminium oxide silicon source be beaten, control slurries pH, then with contain the silica silicon
Source is mixed with beating, then is spray-dried, is roasted, and microsphere particle carrier is obtained, and the microsphere particle carrier is selected from VIB with described
One or both of race, IB the race salting liquid of metal and the salt solution impregnation containing the rare earth element, after drying, roasting
Obtain microsphere particle A；
Wherein, the microsphere particle B is prepared by the following steps to obtain: the silicon source containing the aluminium oxide is beaten into
Glue controls slurries pH, and the oxide selected from one or more of Group IIA, Group IVB and VIII group metal, mixing is then added
Mashing, then is spray-dried, roasts, and obtains microsphere particle carrier, by the microsphere particle carrier use selected from Group IIA, Group IVB and
The salting liquid of one or more of VIII group metal and containing the rare earth element metal salt solution dipping, through drying, roasting
Microsphere particle B is obtained after burning.
12. co-catalyst as claimed in claim 5, wherein the microsphere particle A is prepared by the following steps to obtain: will
Silicon source mashing containing the aluminium oxide, controls slurries pH, is then mixed with beating with the silicon source containing the silica, then is spraying
Dry, roasting, obtains microsphere particle carrier, and the microsphere particle carrier is selected from one of group vib, IB race or two with described
The salting liquid of metal and the salt solution impregnation containing the rare earth element are planted, microsphere particle A is obtained after drying, roasting；
Wherein, the microsphere particle B is prepared by the following steps to obtain: the silicon source containing the aluminium oxide is beaten into
Glue controls slurries pH, and the oxide selected from one or more of Group IIA, Group IVB and VIII group metal, mixing is then added
Mashing, then is spray-dried, roasts, and obtains microsphere particle carrier, by the microsphere particle carrier use selected from Group IIA, Group IVB and
The salting liquid of one or more of VIII group metal and containing the rare earth element metal salt solution dipping, through drying, roasting
Microsphere particle B is obtained after burning.
13. co-catalyst as claimed in claim 6, wherein the microsphere particle A is prepared by the following steps to obtain: will
Silicon source mashing containing the aluminium oxide, controls slurries pH, is then mixed with beating with the silicon source containing the silica, then is spraying
Dry, roasting, obtains microsphere particle carrier, and the microsphere particle carrier is selected from one of group vib, IB race or two with described
The salting liquid of metal and the salt solution impregnation containing the rare earth element are planted, microsphere particle A is obtained after drying, roasting；
Wherein, the microsphere particle B is prepared by the following steps to obtain: the silicon source containing the aluminium oxide is beaten into
Glue controls slurries pH, and the oxide selected from one or more of Group IIA, Group IVB and VIII group metal, mixing is then added
Mashing, then is spray-dried, roasts, and obtains microsphere particle carrier, by the microsphere particle carrier use selected from Group IIA, Group IVB and
The salting liquid of one or more of VIII group metal and containing the rare earth element metal salt solution dipping, through drying, roasting
Microsphere particle B is obtained after burning.
14. co-catalyst as claimed in claim 8, wherein the microsphere particle A is prepared by the following steps to obtain: will
Silicon source mashing containing the aluminium oxide, controls slurries pH, is then mixed with beating with the silicon source containing the silica, then is spraying
Dry, roasting, obtains microsphere particle carrier, and the microsphere particle carrier is selected from one of group vib, IB race or two with described
The salting liquid of metal and the salt solution impregnation containing the rare earth element are planted, microsphere particle A is obtained after drying, roasting；
Wherein, the microsphere particle B is prepared by the following steps to obtain: the silicon source containing the aluminium oxide is beaten into
Glue controls slurries pH, and the oxide selected from one or more of Group IIA, Group IVB and VIII group metal, mixing is then added
Mashing, then is spray-dried, roasts, and obtains microsphere particle carrier, by the microsphere particle carrier use selected from Group IIA, Group IVB and
The salting liquid of one or more of VIII group metal and containing the rare earth element metal salt solution dipping, through drying, roasting
Microsphere particle B is obtained after burning.
15. co-catalyst as claimed in claim 11, wherein when being mixed with beating, adjust the component containing silica
Additional amount, make the heap density 0.85-1.00g/mL of the microsphere particle A；
Wherein, when being mixed with beating, the additional amount of the oxide containing Group IIA is adjusted, the heap density of the microsphere particle B is made
0.75-0.85g/mL。
16. such as the described in any item co-catalysts of claim 12-14, wherein when being mixed with beating, adjust described containing oxidation
The additional amount of the component of silicon makes the heap density 0.85-1.00g/mL of the microsphere particle A；
Wherein, when being mixed with beating, the additional amount of the oxide containing Group IIA is adjusted, the heap density of the microsphere particle B is made
0.75-0.85g/mL。
17. co-catalyst as claimed in claim 11, wherein the pH is 1.2-2.0；The temperature of the drying is 120-
280 DEG C, the dry time is 1-3 hours；
The temperature of the roasting is 500-800 DEG C, and the time of roasting is 1-4 hours.
18. such as the described in any item co-catalysts of claim 12-15, wherein the pH is 1.2-2.0；The temperature of the drying
Degree is 120-280 DEG C, and the dry time is 1-3 hours；
The temperature of the roasting is 500-800 DEG C, and the time of roasting is 1-4 hours.
19. co-catalyst as claimed in claim 16, wherein the pH is 1.2-2.0；The temperature of the drying is 120-
280 DEG C, the dry time is 1-3 hours；
The temperature of the roasting is 500-800 DEG C, and the time of roasting is 1-4 hours.
20. the co-catalyst as described in claim 17 or 19, wherein the temperature of the drying is 180-200 DEG C, when dry
Between be 1-2 hours.
21. co-catalyst as claimed in claim 18, wherein the temperature of the drying is 180-200 DEG C, and the dry time is
1-2 hours.
22. the co-catalyst as described in claim 17 or 19, wherein the temperature of the roasting be 600-700 DEG C, roasting when
Between be 2-3 hours.
23. co-catalyst as claimed in claim 18, wherein the temperature of the roasting is 600-700 DEG C, and the time of roasting is
2-3 hours.
24. co-catalyst described in any one of claim 1-23 reduce FCC` regenerated flue gas in NOx, SOx and CO these
Application in Air Pollutant Emission.
25. application as claimed in claim 24, wherein the co-catalyst is with the ratio of (1:99)-(6:94) and industry
Poising agent is used in mixed way.
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| CN115779924B (en) * | 2021-09-09 | 2024-09-24 | 中国石油化工股份有限公司 | Reducing SO in flue gasxWith NOxCatalyst of (2), preparation method and application thereof, and flue gas SO removalxAnd NOxIs a method of (2) |
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| CN101311248A (en) * | 2007-05-24 | 2008-11-26 | 中国石油化工股份有限公司 | A composition for reducing NOx emission in FCC regeneration flue gas |
| CN101314725A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | Composition for reducing NO<x> discharge in FCC regenerated flue gas |
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