CN106925289A - Reduction of NO in FCC flue gasXContent of catalyst and preparation method thereof - Google Patents
Reduction of NO in FCC flue gasXContent of catalyst and preparation method thereof Download PDFInfo
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- CN106925289A CN106925289A CN201511023529.6A CN201511023529A CN106925289A CN 106925289 A CN106925289 A CN 106925289A CN 201511023529 A CN201511023529 A CN 201511023529A CN 106925289 A CN106925289 A CN 106925289A
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- Prior art keywords
- oxide
- catalyst
- ivth
- rare earth
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000009467 reduction Effects 0.000 title claims description 22
- 239000003546 flue gas Substances 0.000 claims abstract description 43
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 41
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 41
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 14
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 238000007598 dipping method Methods 0.000 claims description 26
- -1 rare earth metal salt Chemical class 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- 229910052723 transition metal Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 102000040350 B family Human genes 0.000 claims description 9
- 108091072128 B family Proteins 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 239000000969 carrier Substances 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 3
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 3
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000002803 maceration Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910001994 rare earth metal nitrate Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
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- 239000010931 gold Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 18
- 238000011069 regeneration method Methods 0.000 abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 15
- 230000008929 regeneration Effects 0.000 abstract description 15
- 229910052809 inorganic oxide Inorganic materials 0.000 abstract 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 29
- 239000007864 aqueous solution Substances 0.000 description 25
- 238000006722 reduction reaction Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- 239000005995 Aluminium silicate Substances 0.000 description 15
- 235000012211 aluminium silicate Nutrition 0.000 description 15
- 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 14
- 230000000052 comparative effect Effects 0.000 description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 12
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 12
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 229910052596 spinel Inorganic materials 0.000 description 11
- 229910052684 Cerium Inorganic materials 0.000 description 10
- 239000012752 auxiliary agent Substances 0.000 description 10
- 238000004523 catalytic cracking Methods 0.000 description 10
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052749 magnesium Inorganic materials 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 239000011029 spinel Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 8
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
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- 229910020068 MgAl Inorganic materials 0.000 description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
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- 238000001816 cooling Methods 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- 150000002823 nitrates Chemical class 0.000 description 5
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- 230000001413 cellular effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- YOSLGHBNHHKHST-UHFFFAOYSA-N cerium manganese Chemical compound [Mn].[Mn].[Mn].[Mn].[Mn].[Ce] YOSLGHBNHHKHST-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001676 gahnite Inorganic materials 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229940121125 oxy clean Drugs 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000011020 pilot scale process Methods 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
- 230000007096 poisonous effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910001954 samarium oxide Inorganic materials 0.000 description 1
- 229940075630 samarium oxide Drugs 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910003451 terbium oxide Inorganic materials 0.000 description 1
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical group O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
- B01D53/565—Nitrogen oxides by treating the gases with solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—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
- 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
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
A catalyst for reducing NOx content in FCC flue gas and a preparation method thereof. The catalyst consists of an acidic inorganic oxide carrier containing alumina and/or silica and layered metal oxides, wherein rare earth metal oxides M and IVB group metal oxides N in the layered metal oxides are inner layers, transition metal oxides X except rare earth and IVB group are outer layers, the mass of the catalyst is 100%, the rare earth metal oxides M are 0.1-12.0%, the mass of the IVB group metal oxides N are 0.1-15%, the mass of the transition metal oxides X except the rare earth and IVB sub-group is 0.1-12.0%, and the balance is the acidic inorganic oxide carrier containing the alumina and/or the silica. The disclosed catalyst has better denitration efficiency and is suitable for oxygen-rich and oxygen-poor regeneration environments.
Description
Technical field
The present invention relates to a kind of oil refining catalyst, and in particular to a kind of denitrating catalyst.
Background technology
Fluid catalytic cracking (FCC) is the important crude oil secondary operation means of China.At present, the raw material of catalyzed cracking processing is increasingly sophisticated, and raw material change is deteriorated again, and the elements such as increasing N, S, heavy metal are contained in raw material.This just makes the NO in regeneration fume from catalytic crackingxDischarge increases.Simultaneously in complete combustive regeneration technique, domestic and international most refinery all uses platinum base CO catalyst, but platinum based catalyst can promote NO in usexGeneration, therefore use platinum agent reduce CO content in smoke while, also significantly increase NOxContent.And NOxThe main component to form acid rain and photochemical fog is not only, and is that regenerative system generation nitre is crisp, crackle is occurred so as to cause the major reason of destruction safety in production and sustainable development.
Standard GB/T 31570-2015《Petroleum refining industry pollutant emission standard》, i.e., from 1 day July in 2015, newly-built enterprise performs the Air Pollutant Emission limit value of the regulation of table 1.
The nitrogen oxides of table 1, sulfur dioxide and granular material discharged standard
Note：Regenerated flue gas pollutant concentration maximum is not to be exceeded 2 times of limit value in table during On Fcc Waste Heat Boiler soot blowing, and each duration not should be greater than 1 hour.
Nitrogen oxides in effluent concentration and nitrogen content and the proportional relation of oxygen concentration in raw material, are in inverse relation with CO content, reaction time, reaction temperature.
NOx∝(N、T、O2、τ、Cat)
Nitrogen content in N- coke
T- regeneration temperatures
O2Oxygen content in-regenerated flue gas
τ-reaction time
Cat- has the catalyst for acting on forward or backwards to NOx generations
At present, following several ways mainly reduce the NO in regeneration fume from catalytic cracking both at home and abroadxContent：Process low nitrogen raw material or carry out raw material denitrogenation pretreatment.
Reaction condition is optimized and controlled to reactor, to reduce catalyst nitrogen content, so as to reduce NO in regenerative processxDischarge.As Kellogg Brown＆Root and Exxon Mobil companies all use gas-solid two phase countercurrent flow regenerator, Excess oxygen content is reduced, reduce main air temperature, in combustion zone injection water vapour etc., NO can be reduced than common regeneratorxDischarge.
Flue gas is processed, main selective catalytic reduction method (SCR), selection noncatalytic reduction (SNCR) and oxidative absorption method etc..In the case of the inapplicable catalyst of SNCR, using reducing agent the NO in flue gasxIt is reduced to N2；SCR is in the presence of oxygen and catalyst, to use NH3NO in reduction flue gasx, generate N2And H2O.NO in SCRxPercent reduction can reach more than 90%.Most common SCR catalyst is V2O5/TiO2, also there is Pt or Pd, often add WO3To increase the intensity and heat endurance of catalyst；Oxidative absorption method is NO oxidations to be converted into using oxidant nitrogen oxides (such as NO for easily being absorbed by absorbent2Or N2O5Deng), corresponding absorbent absorbing and removing, such as LoTOx of Belco Technologies companies exploitation are then used againTMLow-temperature oxidation technique.
(4) additive is used in catalyst regeneration process, respectively by suppressing the generation of NOx in regenerative process and eliminating the NO generated in regenerative processx。NOxThe introducing for reducing additive starts from the mid-90 in 20th century, and it can remarkably promote CO and NOxReaction generation N2And CO2.Such as low platinum base-NO of the brand such as XNOx, OxyClean, CLEANOx of Grace Davison, Engelhard companies block-regulationsxCombustion improver, while second-time burning and CO norm controlling requirements is met, does not increase NO substantiallyxDischarge capacity.
At this stage, being reduced using addition auxiliary agent for domestic report is catalyzed NO in flue gasxContent has following technology, and auxiliary agent is added in regenerator, participates in catalytic cracked regenerated reaction, and NO in catalysis flue gas is reduced during belonging toxContent, is characterized in reducing flue gas NOxProduct can not be influenceed to be distributed while content：
Sinopec Luoyang Petrochemical company and the LDN-1 removal of nitrogen oxide agent of Dushanzi petro-chemical corporation cooperative development, it has CO combustion-supporting and reduces NOxIt is difunctional.The auxiliary agent utilizes macropore active carrier, and aids in rare earth and transition metal isoreactivity metal component, can make NO in regenerated flue gasxContent is reduced to 350mg/m3, removal efficiency reaches 75%, CO contents and maintains 50ppm or so.
The FP-DSN catalyst of Beijing trimerization environmental friendly material joint-stock company exploitation.The auxiliary agent is active component using the oxide or compound of the elements such as La, Ce, Sr, Co, with high strength mullite, aluminum oxide and magnesium aluminate spinel as carrier, can also play reduction SOx60%, NOxMore than 70%, while taking into account the effect of combustion-supporting CO.
A kind of base metal is developed in the triple effect rare earth FCC auxiliary agents RE- II of Peking University's exploitation has combustion-supporting CO, the NO reduced in flue gasxReach more than 70%, improve the triple effect auxiliary agent of light oil yield and total liquid, it with the rare earth-transition metal composite oxides containing more defect sturcture be active component, Al2O3Bead is prepared from as carrier.
Flue gas is processed, main selective catalytic reduction method (SCR), using ammonia the NO in flue gasxIt is reduced to N2.CN201410410827.X provides the low temperature SCR denitration catalyst and preparation method of a kind of titanium-based core shell structure.The catalyst is by composite nanoparticle MnOx-CeO2It is core and TiO2It is the titanium-based core shell structure that shell is constituted, the size range of catalyst is 20-200nm, and wherein tri- kinds of molar ratios of element of Mn, Ce, Ti are 0.05~1：0.05~1：1.Its preparation method mainly comprises the following steps：(1) cerous nitrate and manganese nitrate solution are mixed, is added dropwise over sodium hydroxide solution, then mixed liquor is transferred in water heating kettle, by reaction, centrifugation, washing, dry, calcining, obtained a nanometer MnOx-CeO2Particulate matter；(2) claim by constructing titanium-based core shell structure, by catalyst centrally through TiO preparing the Core-shell Structure Nanoparticles patented technologies with CTAB as surfactant, in the reverse micro emulsion that n-amyl alcohol is as cosurfactant, hexamethylene is as oil phase2Shell is protected, and reduces activated centre with SO in flue gas2The probability of contact, so as to avoid activated centre by SO2Corrode and irreversible poisoning occurs.
Flue gas is processed, main selective catalytic reduction method (SCR), using ammonia the NO in flue gasxIt is reduced to N2。
CN201210445095.9 discloses a kind of middle medium/low-temperature core-shell denitration catalyst and preparation method and application, primary raw material composition is the soluble-salt of titanium-based nano pipe, the soluble-salt of cerium and manganese, the oxide of the carrier shell of titanium-based nano pipe composition catalyst, cerium and manganese constitutes the active nanoparticles kernel of catalyst.Ce elements and manganese element sum and the mol ratio of titanium elements are 0.02~0.12:1, cerium manganese mol ratio ＞ 0.5, ＜ 0.25, between 0.25~0.5 when the catalyst middle temperature, low temperature and middle low-temperature space activity it is preferable.The soluble-salt dipping of immersion treatment, the soluble-salt of addition cerium and manganese is carried out to titanium-based nano pipe with organic solvent, drying, roasting obtains middle medium/low-temperature core-shell denitration catalyst.The catalyst has broad application prospects in the solid-state poisonous component content such as industrial furnace tail gas and biomass fuel power-plant flue gas waste gas pollution control and treatment high.
But the catalyst of this flue gas reduction NOX can not be directly added into Fcc Regenerator, and NOx is reacted during the catalyst of one side flue gas reduction NOX must make cellular or other shapes, with flue gas；Reduced using CO more than another aspect catalytic cracking chimney flue gas.
W. R. Grace ＆ Co is disclosed in CN200380107194.5, US7906015B, CN200380107164.4, CN200680009505.8 for reducing in partially or incompletely combustion catalysis cracking process, the vapour phase reduction nitrogen class material and the composition of NOx produced preferably in fluidized catalytic process.Said composition is substantially free of the acidic metal oxide of zeolite comprising (i), (ii) alkali metal, alkaline-earth metal and their mixture, (iii) oxygen storage components and (iv) noble metal component, preferably rhodium or iridium and their mixture.Preferably, using said composition as the independent additive particle circulated together with circulation FCC catalyst residual oil.As waste gas stream is from FCC regenerating furnaces to CO boilers, the reduction of vapour phase reduction nitrogen class material and NOx emission declines overall NOx in the outflow waste gas of FCC regenerating furnaces that partially or incompletely burns, thus as CO is oxidized to CO2, it is less amount of reduction nitrogen class material be oxidized to NOx.But it can only be used in the catalytic cracking process of oxygen deprivation, i.e., alkali metal is preferably used in the catalytic cracking process for partially or incompletely burning, and the invention and does active component, especially Na, and alkali metal can influence the activity of denitrating catalyst.
To sum up, the denitration auxiliary agent of major company's exploitation both at home and abroad at present, generally using noble metal and denitration efficiency is not high, because of the present circumstance, is eager to develop a kind of efficient auxiliary agent of denitration efficiency, and be applicable oxygen-enriched and oxygen deprivation regenerative environ-ment.
The content of the invention
The main object of the present invention is to provide NO in reduction regeneration fume from catalytic crackingxThe catalyst of content, the catalyst has preferable denitration efficiency, and is applicable oxygen-enriched and oxygen deprivation regenerative environ-ment.
The catalyst of NOx content in reduction FCC flue gases disclosed in this invention,Described catalyst is made up of the metal oxide of the acid mineral oxide carrier containing aluminum oxide and/or silica and layering,The metal oxide middle rare earth metal oxide M and the IVth B family metal oxides N of described layering are internal layer,Transition metal oxide X in addition to rare earth and the IVth B races is outer layer,In terms of catalyst quality 100%,Rare-earth oxide M is 0.1~12.0%,It is preferred that 1.0~12.0,More preferably 2.0~10.0%,IVth B family metal oxides N is 0.1~15%,It is preferred that 1.0~12.0%,More preferably 2.0~12.0%,Transition metal oxide X 0.1~12.0% in addition to rare earth and the IVth B subgroups,It is preferred that 1.0~12.0%,More preferably 2.0~12.0%,The balance of acid mineral oxide carrier containing aluminum oxide and/or silica.
The catalyst of NOx content in reduction FCC flue gases disclosed in this invention, the acid mineral oxide carrier containing aluminum oxide and/or silica includes aluminum oxide, silica, or its mixture, or containing aluminum oxide and/or silica composite material, or spinelle or houghite containing aluminum oxide.The general knowledge that these materials are known in the art, such as common alumina silica composite has various forms of clays, typically there are kaolin, perlite, concave convex rod, diatomite, montmorillonite, rectorite, galapectite, these materials are natural alumina silica composite, and it is layer structure.Also having some composites containing aluminum oxide for synthesizing can be used for the present invention, for example, can also be used for the present invention in the composite disclosed in CN201110267805.9, CN201110134042.0.
The catalyst of NOx content, the described spinelle containing aluminum oxide or the material of houghite, typically there is magnesium aluminate spinel, gahnite, nickel aluminate in reduction FCC flue gases disclosed in this invention.
The catalyst of NOx content in reduction FCC flue gases disclosed in this invention, described rare-earth oxide is the oxide of the lanthanide series metal in IIIB, its existence form is the form of simple metals oxide form or mixed rare-earth oxide, specifically, rare-earth oxide of the present invention includes but is not limited to cerium oxide, samarium oxide, praseodymium oxide, europium oxide, lanthana, terbium oxide and their mixture, in these oxides, rare earth preferably exists with trivalent form, tetravalent form.
The catalyst of NOx content in reduction FCC flue gases disclosed in this invention, the oxide existence form simple metals oxide form of the IVth described B B metals, specifically, IVth B B metal oxides of the present invention include but is not limited to titanium oxide, zirconium oxide, hafnium oxide, oxidation Lu and their mixture, in these oxides, metal preferably exists with trivalent form, tetravalent form.
The oxide existence form simple metals oxide or the form of mixed-metal oxides of the IVth described B B metals, specifically, IVth B B metal oxides of the present invention include but is not limited to titanium oxide, zirconium oxide, hafnium oxide, oxidation Lu and their mixture, in these oxides, metal preferably exists with trivalent form, tetravalent form.
The catalyst of NOx content in reduction FCC flue gases disclosed in this invention, the described metal oxide in addition to rare earth and the IVth B subgroups refers to the metal oxide selected from one or more metal in I B, II B, V B, VI B, VII B, VIII, preferably I B, II B, VI B, VII B family metal oxides, it is preferred that I B, V B, VI B, VII B family metal oxides, I B, III B, V B more preferably in addition to noble metal, VI B, VII B family metal oxides, more preferably one or more from vanadium, manganese, iron, copper, zinc, molybdenum, tungsten, silver.Transition metal oxide in addition to rare earth and the IVth B B metals, as long as the oxide of these metals can just meet requirement of the invention, but the present invention form that preferably it is present is that the highest price of metal or the form of secondary high oxide are present.The highest price of described metal refers to that, when the metal in metal oxide has various valence states, metal is preferentially from the metal oxide of highest valence state in catalyst of the invention；Time high price of described metal refers to that, when the metal in metal oxide has various valence states, metal is preferentially from the metal oxide for being only below highest valence state in catalyst of the invention.Particularly, by taking the oxide of the iron in transition metal as an example, highest price ferriferous oxide is ferroso-ferric oxide, and secondary high price ferriferous oxide is di-iron trioxide；Highest price tungsten oxide is tungstic acid in the oxide of tungsten, and secondary high price tungsten oxide is tungsten dioxide, and the general knowledge of these this chemical fields, the present invention is not enumerated to these materials.
The catalyst of NOx content, 0.00005~0.002g/m of supported metal oxide content in reduction FCC flue gases disclosed in this invention2。
The invention also discloses the preparation method of the catalyst, including：The solution containing rare earth metal salt and the IVth B races slaine is prepared, the acid mineral oxide carrier containing aluminum oxide and/or silica is impregnated, pH value 3~6.5 is adjusted with acidic materials, preferably 4.5~6.0, obtain M-N- carriers；Again with the solution impregnation M-N- carriers of the transition metal salt in addition to rare earth and the IVth B races, dry, thermally decompose, be calcined, obtain catalyst.
Described rare earth metal salt is one or more in rare-earth metal nitrate, acetate.
The described transition metal salt in addition to rare earth and IV B is one or more in nitrate, acetate, the oxometallic acid ammonium salt of the transition metal in addition to rare earth.
The preparation method of catalyst of the present invention, when the described transition metal salt in addition to rare earth and the IVth B races is oxometallic acid ammonium salt, maceration extract preferably adjusts pH value of solution 8~14, preferably 9~12 with alkaline matter.
Preparation method disclosed in this invention, drying therein, is roasted to technological means known in those skilled in the art, and the present invention recommends, in 100~150 DEG C of dryings 3~4 hours, to be calcined 2~6 hours, preferably 3~4 hours at 500~750 DEG C.
Preparation method disclosed in this invention, thermal decomposition therein is thermally decomposed 2~3 hours preferably in 200~300 DEG C of air.
Preparation method disclosed in this invention, when described carrier is aluminum oxide, gama-alumina and/or its presoma boehmite, boehmite, fibrous boehmite, nano bar-shape boehmite can be added in preparation, one or more of nano lamellar boehmite, preferred vector is shaped as 40~80 μm of microspheroidals, 100~200m of specific surface area2/g。
Preparation method disclosed in this invention, described acidic materials are inorganic acid and/or organic acid, and one or more in the preferred oxalic acid of organic acid, citric acid, acetic acid, described inorganic acid is monoacid or binary acid, monoacid is selected from hydrochloric acid and/or nitric acid, and described binary acid is sulfuric acid.
Described alkaline matter is selected from one or more in ammoniacal liquor, ammonium phosphate, diammonium hydrogen phosphate, ammonium carbonate, ammonium hydrogen carbonate.
The catalyst is used for FCC reaction-regeneration systems, in FCC catalyst regenerative process, when regeneration temperature is at 600~800 DEG C, when regeneration atmosphere is oxygen-enriched or oxygen deprivation, can effectively reduce NO in regenerated flue gasxContent.
Beneficial effects of the present invention：
Catalyst disclosed in this invention, with acidic oxide as carrier, its metal oxide is internal layer first by rare-earth oxide and the IVth B races, then using the transition metal in addition to rare earth and the IVth B races as outer layer, different metal is presented the state of different shell distributions, this improves the decentralization of metal oxide component so that no matter catalyst of the present invention regeneration atmosphere is oxygen-enriched or oxygen deprivation, can effectively reduce NO in regenerated flue gasxContent more than 80%, while catalytic cracking production has preferable product slates.Catalyst disclosed in this invention, in laboratory room small-sized reaction unit, simulates and experiment has been carried out on industrial pilot scale FCC apparatus and commercial scale FCC apparatus investigates, and shows while having that CO is combustion-supporting and reduction NO concurrentlyxContent function, under conditions of oxygen deprivation regeneration, can effectively reduce in regenerated flue gas CO contents up to more than 85%.And the preparation method of catalyst disclosed in this invention, the immersion condition of metal is controlled in preparation process, the catalyst that can be just layered, the preparation process of catalyst is simply easily achieved；And metal component is evenly distributed.Catalyst disclosed in this invention can be used in conjunction with catalytic cracking catalyst, add in catalytic cracked regenerated device, have a good application prospect.
Brief description of the drawings
Fig. 1 is the catalyst thing phasor (XRD diffraction patterns) prepared by embodiment 1, there is strong diffraction maximum in 35 °, 45 °, 65 ° in the 2theta of catalyst, it is the thing phase of the alumina support of pure phase, the metal oxide of the outer layer of this explanation catalyst is uniformly distributed in oxide carrier.
Fig. 2 is the catalyst thing phasor (XRD diffraction patterns) prepared by comparative example 3, there is strong diffraction maximum in 32 °, 35 °, 42 °, 45 °, 55 °, 65 ° in the 2theta of catalyst, wherein 35 °, 45 °, 65 ° is the thing phase of the alumina support of pure phase, 32 °, 42 °, 55 ° is the thing phase of metal oxide, the metal oxide of the outer layer of this explanation catalyst can not be uniformly distributed in oxide carrier, form the oxide of big crystal grain.
Specific embodiment
Embodiments of the invention are elaborated below：The present embodiment is implemented under premised on technical solution of the present invention; give detailed implementation method and process; but protection scope of the present invention is not limited to following embodiments, the technological parameter of unreceipted actual conditions in the following example, generally according to normal condition.
Raw material sources：γ-Al2O3 are purchased from Shandong Aluminum Plant；
Kaolin selects No. 2 soil purchased from China Kaolin Co., Ltd's Suzhou machine.
Yttrium nitrate, cerous nitrate, lanthanum nitrate, lanthanum chloride, acetic acid, copper nitrate, manganese nitrate, zinc nitrate, cerous nitrate, silver nitrate, ammonium paratungstate, ammonium molybdate, oxalic acid, glacial acetic acid are purchased from Sichuan Xilong Chemical Co., Ltd..
The nitrate of cerium-rich rare earth, manufacturer is Catalyst Factory of Lanzhou Petrochemical Company industrial goods.
NOxContent analysis method：Using the flue gas analyzers of Figure 35 0 carry out NOXAssay, calibrating gas therein is 1000ppmNOx；
CO content analysis methods：The auspicious online flue gas analyzer of 2000 model is matched using magnificent peak to be measured, calibrating gas therein is 1000ppm CO；
The tester of XRD diffraction：Rigaku D/MAX 2200PC.
Tenor tester：Rigaku ZSX primus type XRF analysis instruments.
Specific surface area：Using the type N of Mike 30002Adsorption instrument is tested.
Embodiment 1
Take dried 100g γ-Al2O3Make carrier.The 2.0mol/L yttrium nitrates and nitric acid aqueous zirconium of 17ml are prepared and taken, γ-Al are added2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain Y-Zr-Al2O3。
1.0mol/L copper nitrates, manganese nitrate and zinc nitrate aqueous solution 27ml are prepared and taken, Y-Zr-Al is added2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain the catalyst for reducing NOx content in FCC flue gases.
Carrier specific surface area is 200g/m2, supported metal oxide content is 0.000704g/m2
Embodiment 2
Microspheroidal kaolin preparation method prepares microspheroidal kaolin with reference to the embodiment 1 of CN200410091494.5.
Take after above-mentioned microspheroidal kaolin is dried through 120 DEG C and weigh 100g and make carrier.The zirconium nitrate solution of the cerium-rich rare earth nitrate of the 2.0mol/L of 17ml and the 1.0mol/L of 13ml is prepared and taken, microspheroidal kaolin dipping is added, after placing 2.5 hours, dried 3 hours in 100 DEG C, 280 DEG C thermally decompose 2.5 hours, and 600 DEG C are calcined 2 hours, obtain Ce-Y-Zr- microspheroidal kaolin.
The 1.0mol/L ammonium molybdate aqueous solutions of 27ml are prepared and taken, pH value 12 is adjusted with ammoniacal liquor, add dipping, after placing 2 hours, dried in 120 DEG C 3 hours, 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, are reduced the catalyst of NOx content in FCC flue gases.
Embodiment 3
Take after magnesium aluminate spinel is dried through 120 DEG C and weigh 100g and make carrier.2.0mol/L cerous nitrates, the titanium tetrachloride aqueous solution of the 1.0mol/L of the 1.0mol/L lanthanum nitrates and 11ml of 17ml of 17ml are prepared and taken, MgAl is added2O4Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain Ce-La-MgAl2O4。
1.0mol/L copper nitrates, manganese nitrate and the zinc nitrate aqueous solution of 27ml are prepared and taken, Ce-La-MgAl is added2O4Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, are reduced the catalyst of NOx content in FCC flue gases.
Embodiment 4
Take γ-Al2O3100g is weighed after being dried through 120 DEG C make carrier.2.0mol/L cerous nitrates, the titanium tetrachloride aqueous solution of the 1.2mol/L of the 1.2mol/L lanthanum chlorides and 18ml of 15ml for preparing and taking 15ml are prepared and taken, γ-Al are added2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain Ce-La-Ti-Al2O3。
The 0.8mol/L ammonium paratungstate aqueous solution for preparing and taking 25ml is prepared and taken, pH value 12 is adjusted with ammoniacal liquor, add Ce-La-Ti-Al2O3Dipping, after placing 2 hours, dries 3 hours in 150 DEG C, and 250 DEG C thermally decompose 3.2 hours, and 600 DEG C are calcined 2 hours, are reduced the catalyst of NOx content in FCC flue gases.
Carrier specific surface area is 200g/m2, supported metal oxide content is 0.001008g/m2
Embodiment 5
Take after microspheroidal magnesium aluminate spinel is dried through 120 DEG C and weigh 100g and make carrier.The 1.2mol/L nitric acid aqueous zirconiums of the 2.0mol/L yttrium nitrates of 12ml, the 2.0mol/L cerous nitrates of 12ml and 13ml are prepared and taken, MgAl is added2O4Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain mischmetal-Zr-MgAl2O4。
The 0.2mol/L zinc nitrate aqueous solutions of the 1.0mol/L silver nitrates of 27ml, the 0.5mol/L manganese nitrates of 27ml and 26ml are prepared and taken, mischmetal-Zr-MgAl is added2O4Dipping, avoid light place is dried 3 hours after 2 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain the catalyst for reducing NOx content in FCC flue gases.
Embodiment 6
Take γ-Al2O3100g is weighed after being dried through 120 DEG C make carrier.The 3.0mol/L tetraethyl titanates of 3.0mol/L cerous nitrate aqueous solution 17ml and 17ml are prepared and taken, γ-Al are added2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain Ce-Ti-Al2O3。
Prepare and take to prepare and take and prepare and take 1.0mol/L ammonium paratungstates and ammonium molybdate aqueous solution 27ml, pH value 12 is adjusted with ammoniacal liquor, add Ce-Ti-Al2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain the catalyst for reducing NOx content in FCC flue gases.
Comparative example 1
Catalyst is prepared with reference to US6280607 methods.
Take dried 100g γ-Al2O3Make carrier.2.2mol/L calcium nitrate aqueous solution 20.1ml are added, deionized water 28ml is added, after being well mixed, by 100g microballoon γ-Al2O3Immersion is stirred evenly, and is placed 2 hours.Then dried at 110 DEG C 3 hours, 260 DEG C thermally decompose 2 hours, and 700 DEG C are calcined 3 hours, obtain being loaded with the γ-Al of calcium oxide after cooling2O3。
The 2.0mol/L yttrium nitrate aqueous solutions of 17ml are prepared and take, addition is loaded with the γ-Al of calcium oxide2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain being loaded with the γ-Al of strontium oxide strontia, yittrium oxide2O3。
1.0mol/L copper nitrates, manganese nitrate and zinc nitrate aqueous solution 27ml are prepared and take, addition is loaded with the γ-Al of strontium oxide strontia, yittrium oxide2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain catalyst.
Comparative example 2
Microspheroidal kaolin preparation method prepares microspheroidal kaolin with reference to the embodiment 1 of CN200410091494.5.
Take after microspheroidal kaolin is dried through 120 DEG C and weigh 100g and make carrier.2.3mol/L magnesium nitrate aqueous solution 30.1ml are added in beaker, deionized water 20ml is added, after being well mixed, the immersion of 100g microspheroidals kaolin is stirred evenly, placed 3 hours.Then dried at 150 DEG C 2 hours, 300 DEG C thermally decompose 2 hours, and 600 DEG C are calcined 3 hours, obtain being loaded with the kaolin microsphere of magnesia after cooling.
The cerium-rich rare earth nitrate solution of the 2.0mol/L of 17ml is prepared and taken, Mg- kaolin dipping is added, after placing 2.5 hours, dried 3 hours in 100 DEG C, 280 DEG C thermally decompose 2.5 hours, and 600 DEG C are calcined 2 hours, obtain being loaded with the kaolin microsphere of magnesia and cerium-rich rare earth oxide.
The 1.0mol/L ammonium molybdate aqueous solutions of 27ml are prepared and taken, pH value 12 is adjusted with ammoniacal liquor, addition is loaded with the kaolin microsphere dipping of magnesia and cerium-rich rare earth oxide, after placing 2 hours, dried in 120 DEG C 3 hours, 250 DEG C thermally decompose 3 hours, 600 DEG C are calcined 2 hours, obtain catalyst.
Carrier specific surface area is 180g/m2, supported metal oxide content is 0.00555g/m2
Comparative example 3
Take after magnesium aluminate spinel is dried through 120 DEG C and weigh 100g and make carrier.2.0mol/L strontium nitrate aqueous solution 30ml are added, deionized water 28ml is added, after being well mixed, the immersion of 100g microballoons magnesium aluminate spinel is stirred evenly, placed 2 hours.Then dried at 130 DEG C 3 hours, 260 DEG C thermally decompose 2.1 hours, and 700 DEG C are calcined 3 hours, obtain being loaded with the magnesium aluminate spinel of strontium oxide strontia after cooling.
The 2.0mol/L cerous nitrates of 17ml and the 1.0mol/L lanthanum nitrate aqueous solutions of 17ml are prepared and taken, Sr-MgAl is added2O4Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain being loaded with the magnesium aluminate spinel of strontium oxide strontia, cerium oxide and lanthana.
1.0mol/L copper nitrates, manganese nitrate and the zinc nitrate aqueous solution of 27ml are prepared and take, addition is loaded with the magnesium aluminate spinel dipping of strontium oxide strontia, cerium oxide and lanthana, after placing 2 hours, dried 3 hours in 120 DEG C, 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain catalyst.
Comparative example 4
Take γ-Al2O3100g is weighed after being dried through 120 DEG C make carrier.3.2mol/L magnesium nitrate aqueous solution 23.3ml are prepared and taken, deionized water 28ml is added, after being well mixed, by 100g microspheroidal γ-Al2O3Immersion is stirred evenly, and is placed 2 hours.Then dried at 140 DEG C 3 hours, 250 DEG C thermally decompose 2 hours, and 700 DEG C are calcined 3 hours, obtain being loaded with the γ-Al of magnesia after cooling2O3。
The 1.2mol/L lanthanum chloride solutions of the 2.0mol/L cerous nitrates and 15ml that prepare and take 15ml are prepared and take, addition is loaded with the γ-Al of magnesia2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain being loaded with the γ-Al of magnesia, cerium oxide and lanthana2O3。
The 0.8mol/L ammonium paratungstate aqueous solution for preparing and taking 25ml is prepared and taken, pH value 12 is adjusted with ammoniacal liquor, addition is loaded with the γ-Al of magnesia, cerium oxide and lanthana2O3Dipping, after placing 2 hours, dries 3 hours in 150 DEG C, and 250 DEG C thermally decompose 3.2 hours, and 600 DEG C are calcined 2 hours, obtain catalyst.
Comparative example 5
Take γ-Al2O3100g is weighed after being dried through 120 DEG C make carrier.The 3.0mol/L tetraethyl titanates of 3.0mol/L cerous nitrate aqueous solution 17ml and 17ml are prepared and taken, γ-Al are added2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain Ce-Ti-Al2O3。
Prepare and take to prepare and take and prepare and take 1.0mol/L ammonium paratungstates and ammonium molybdate aqueous solution 27ml, add Ce-Ti-Al2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain the catalyst for reducing NOx content in FCC flue gases.
Comparative example 6
Embodiment 1 of the sample preparation methods with reference to CN1345629A.
Using γ-Al2O3It is carrier, 40-80 μm of its granularity accounts for 70%, and it is that, less than 20%, water absorption rate is 0.55 to be more than 80 μm.Preparing for catalyst is as follows：
(1) Ce (NO of 2.00mol/L are taken3)3Al (the NO of aqueous solution 66.8ml and 2.00mol/L3)3Again with addition of 15.8g citric acids (C after aqueous solution 8.3ml mixing6H8O7·H2) and 190.0ml water is complexed it O.Above-mentioned γ-Al are impregnated with this complex solution2O3 500g。
The dipping thing of gained is placed in into 120 DEG C of heat to dry 2 hours, 280 DEG C thermally decompose 2 hours, then products therefrom is placed in 680 DEG C and activated 3 hours, solids Ce-Al-O/ γ-Al are obtained after cooling2O3。
(2) Cu (NO of 3.06mol/L are taken3)2Al (the NO of aqueous solution 188.0ml and 2.14mol/L3)3Aqueous solution 43.1ml, 69.5g citric acids are added after mixing and is well mixed is complexed it.Above-mentioned solids Ce-Al-O/ γ-Al2O3 are impregnated with this complex solution.Dipping thing dries 3 hours in 110 DEG C of heat, and 250 DEG C thermally decompose 2.5 hours, products therefrom is placed in 580 DEG C again and activates 2 hours to obtain catalyst Cu-Al-O/Ce-Al-O/ γ-Al2O3。
Comparative example 7
Blank test：Industrial FCC catalyst (LDC-200) (Catalyst Factory of Lanzhou Petrochemical Company production)
Embodiment 7
After according to addition content 1.5% (m), the catalyst prepared by embodiment 1~6, comparative example 1~6 is mixed with industrial FCC catalyst (LDC-200) (Catalyst Factory of Lanzhou Petrochemical Company production) respectively as auxiliary agent, tested on DCR type riser catalytic crackings evaluating apparatus (production of Grace companies of the U.S.) respectively, wherein embodiment 1~3 and comparative example 1~3 and comparative example 7 is oxygen deprivation regeneration, O2Content is 0.06v%, and embodiment 4~6 and comparative example 4~6 are oxygen enrichment regeneration, O2Content is 2.1v%, and specific experimental condition is shown in Table 2, and result of the test is shown in Table 3.
Table 2FCCU operating conditions
| Feedstock oil | Xinjiang decompressed wax oil：Decompression residuum=7:3 |
| Reaction temperature, DEG C | 500 |
| Oil ratio, m/m | 6.0 |
| Reaction time, s | 3 |
| Regeneration temperature, DEG C | 690 |
| Promoter addition | The 1.5% of FCC catalyst reserve |
Influence of the different auxiliary agents of table 3 to catalytic cracking reaction flue gas NOx and CO
Comparative example 1~7 and the experimental result of embodiment 1~6, show：This inorganic refractory oxides supported alkaline earth metal, rare earth metal, compound transition metal oxide reduce NO in flue gas in the case of addition content is for the 1.5m% of FCC catalystxMore than 80%, under conditions of oxygen deprivation regeneration, CO reduction amplitudes more than 85%.
Claims (15)
1. in a kind of reduction FCC flue gases NOx content catalyst, it is characterised in that described catalyst
It is made up of the metal oxide of the acid mineral oxide carrier containing aluminum oxide and/or silica and layering,
The metal oxide middle rare earth metal oxide M and the IVth B family metal oxides N of described layering are interior
Layer, the transition metal oxide X in addition to rare earth and the IVth B races are outer layer, in terms of catalyst quality 100%,
Rare-earth oxide M is 0.1~12.0%, and the IVth B family metal oxides N is 0.1~15%, except dilute
Soil and the IVth B subgroups outside transition metal oxide X be 0.1~12.0%, it is balance of containing aluminum oxide and/
Or the acid mineral oxide carrier of silica.
2. catalyst according to claim 1, it is characterised in that described rare-earth oxide M
It is 1.0~12.0%, the IVth B family metal oxides N is 1.0~12.0%, in addition to rare earth and the IVth B subgroups
Transition metal oxide X be 1.0~12.0%.
3. catalyst according to claim 1, it is characterised in that described rare-earth oxide M
It is 2.0~10.0%, the IVth B family metal oxides N is 2.0~12.0%, in addition to rare earth and the IVth B subgroups
Transition metal oxide X be 2.0~12.0%.
4. catalyst according to claim 1 and 2, it is characterised in that the IVth described B races metal
Oxide be selected from titanium oxide, zirconium oxide, hafnium oxide, oxidation Lu and their mixture.
5. catalyst according to claim 1 and 2, it is characterised in that described except rare earth and the IVth
The outer metal oxide of B subgroups refers to I B, II B, V B, VI B, VII B, VIII metal oxide.
6. catalyst according to claim 5, it is characterised in that described except rare earth and the IVth B pairs
Metal oxide is selected from the one kind or several in vanadium, manganese, iron, copper, zinc, molybdenum, tungsten, the oxide of silver outside race
Kind.
7. catalyst according to claim 5, it is characterised in that described except rare earth and the IVth B pairs
The form of the presence of metal oxide is the highest price or secondary high oxide of metal outside race.
8. catalyst according to claim 1 and 2, it is characterised in that it is described containing aluminum oxide and/
Or the acid mineral oxide carrier of silica is selected from aluminum oxide, silica, or its mixture, or containing aerobic
Change aluminium and/or silica composite material, or spinelle or houghite containing aluminum oxide.
9. catalyst according to claim 1 and 2, it is characterised in that in described catalyst, carrier
Upper 0.00005~0.002g/m of metal oxide content2。
10. a kind of preparation method of the catalyst described in claim 1, it is characterised in that the preparation method
For：The solution containing rare earth metal salt and the IVth B races slaine is prepared, dipping contains aluminum oxide and/or oxidation
The acid mineral oxide carrier of silicon, with acidic materials adjust pH value 3~6.5, preferably 4.5~6.0, obtain
M-N- carriers；Again with the solution impregnation M-N- carriers of the transition metal salt in addition to rare earth and the IVth B races, dry,
Thermal decomposition, roasting, obtain catalyst.
The preparation method of the catalyst described in a kind of 11. claims 10, it is characterised in that described rare earth
Slaine is one or more in rare-earth metal nitrate, acetate；The IVth described B group 4 transition metals
Salt is one or more in nitrate, the acetate of the IVth B races metal；It is described except rare earth and the IVth B
Transition metal salt is nitrate, acetate, the metal oxygen of the transition metal salt in addition to rare earth and the IVth B races outside race
One or more in acid ammonium salt.
12. according to the preparation method described in claim 10, it is characterised in that described acidic materials are inorganic
Acid and/or organic acid.
13. preparation methods according to claim 10, it is characterised in that described thermal decomposition exists
Thermally decomposed 2~3 hours in 200~300 DEG C of air.
14. preparation methods according to claim 10, it is characterised in that described containing except rare earth and
When transition metal salt is oxometallic acid ammonium salt outside IV B races, transition metal salt is gold in addition to rare earth and the IVth B races
The maceration extract for belonging to oxygen acid ammonium salt adjusts pH value of solution 8~14, preferably 9~12 with alkaline matter.
15. preparation methods according to claim 14, it is characterised in that described alkaline matter is selected from
One or more in ammoniacal liquor, ammonium phosphate, diammonium hydrogen phosphate, ammonium carbonate, ammonium hydrogen carbonate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252283A (en) * | 2019-06-14 | 2019-09-20 | 湖北中和普汇环保股份有限公司 | A kind of preparation method and applications of modified SCR catalyst |
| CN112354358A (en) * | 2020-09-17 | 2021-02-12 | 山东骏飞环保科技有限公司 | Catalytic cracking oxygen-poor regeneration denitration agent and preparation method thereof |
| CN114525160A (en) * | 2022-03-18 | 2022-05-24 | 宁波中科远东催化工程技术有限公司 | Coke heat intensity auxiliary material and preparation process thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6143167A (en) * | 1995-05-05 | 2000-11-07 | W. R. Grace & Co.-Conn. | NOx reduction compositions for use in FCC processes |
| US20030098259A1 (en) * | 2001-11-23 | 2003-05-29 | Engelhard Corporation | NOx reduction composition for use in FCC processes |
| CN1909962A (en) * | 2004-01-23 | 2007-02-07 | 恩格哈德公司 | NOx reduction composition for use in FCC processes |
| CN101422736A (en) * | 2007-11-02 | 2009-05-06 | 南化集团研究院 | Catalyst for removing nitrogen oxide in FCC stack gas at low temperature and production method thereof |
| 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) |
| CN104209129A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Used for reducing NO in FCC flue gasXContent of catalyst and application |
| CN105148928A (en) * | 2015-08-17 | 2015-12-16 | 中国石油大学(北京) | Water-resistant and sulfur-resistant powder catalyst for flue gas denitrification, preparation method and application of water-resistant and sulfur-resistant powder catalyst |
-
2015
- 2015-12-30 CN CN201511023529.6A patent/CN106925289A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6143167A (en) * | 1995-05-05 | 2000-11-07 | W. R. Grace & Co.-Conn. | NOx reduction compositions for use in FCC processes |
| US6280607B1 (en) * | 1995-05-05 | 2001-08-28 | W R Grace & Co.-Conn. | NOx reduction compositions for use in FCC processes |
| US20030098259A1 (en) * | 2001-11-23 | 2003-05-29 | Engelhard Corporation | NOx reduction composition for use in FCC processes |
| CN1909962A (en) * | 2004-01-23 | 2007-02-07 | 恩格哈德公司 | NOx reduction composition for use in FCC processes |
| CN101422736A (en) * | 2007-11-02 | 2009-05-06 | 南化集团研究院 | Catalyst for removing nitrogen oxide in FCC stack gas at low temperature and production method thereof |
| 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) |
| CN104209129A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Used for reducing NO in FCC flue gasXContent of catalyst and application |
| CN105148928A (en) * | 2015-08-17 | 2015-12-16 | 中国石油大学(北京) | Water-resistant and sulfur-resistant powder catalyst for flue gas denitrification, preparation method and application of water-resistant and sulfur-resistant powder catalyst |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252283A (en) * | 2019-06-14 | 2019-09-20 | 湖北中和普汇环保股份有限公司 | A kind of preparation method and applications of modified SCR catalyst |
| CN112354358A (en) * | 2020-09-17 | 2021-02-12 | 山东骏飞环保科技有限公司 | Catalytic cracking oxygen-poor regeneration denitration agent and preparation method thereof |
| CN114525160A (en) * | 2022-03-18 | 2022-05-24 | 宁波中科远东催化工程技术有限公司 | Coke heat intensity auxiliary material and preparation process thereof |
| CN114525160B (en) * | 2022-03-18 | 2023-08-01 | 宁波中科远东催化工程技术有限公司 | Coke heat strong auxiliary material and preparation process thereof |
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