CN109126862A - It is a kind of accelerate synthesis CHA structure molecular sieve method and its catalyst NH3-SCR reaction in application - Google Patents
It is a kind of accelerate synthesis CHA structure molecular sieve method and its catalyst NH3-SCR reaction in application Download PDFInfo
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- CN109126862A CN109126862A CN201810948803.8A CN201810948803A CN109126862A CN 109126862 A CN109126862 A CN 109126862A CN 201810948803 A CN201810948803 A CN 201810948803A CN 109126862 A CN109126862 A CN 109126862A
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- China
- Prior art keywords
- molecular sieve
- cha structure
- promotor
- structure molecular
- solution
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 100
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000012456 homogeneous solution Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims description 11
- 239000002585 base Substances 0.000 claims description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 11
- 239000010457 zeolite Substances 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 150000002484 inorganic compounds Chemical class 0.000 claims description 9
- 229910010272 inorganic material Inorganic materials 0.000 claims description 9
- 150000002894 organic compounds Chemical class 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- 239000002671 adjuvant Substances 0.000 claims description 7
- -1 alkali metal salt Chemical class 0.000 claims description 6
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001447 alkali salts Chemical class 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- RJIWZDNTCBHXAL-UHFFFAOYSA-N nitroxoline Chemical compound C1=CN=C2C(O)=CC=C([N+]([O-])=O)C2=C1 RJIWZDNTCBHXAL-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- 238000002441 X-ray diffraction Methods 0.000 abstract description 4
- 238000005470 impregnation Methods 0.000 abstract description 4
- 238000001338 self-assembly Methods 0.000 abstract description 4
- 238000011156 evaluation Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 38
- 238000006116 polymerization reaction Methods 0.000 description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 9
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- 239000012752 auxiliary agent Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 230000008878 coupling Effects 0.000 description 7
- 238000010168 coupling process Methods 0.000 description 7
- 238000005859 coupling reaction Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000012018 catalyst precursor Substances 0.000 description 6
- 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 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 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 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000013618 particulate matter Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 239000007836 KH2PO4 Substances 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DBRMBYFUMAFZOB-UHFFFAOYSA-N molybdenum nitric acid Chemical compound [Mo].[N+](=O)(O)[O-] DBRMBYFUMAFZOB-UHFFFAOYSA-N 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TYOIKSXJQXGLFR-UHFFFAOYSA-N niobium nitric acid Chemical compound [Nb].[N+](=O)(O)[O-] TYOIKSXJQXGLFR-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100001143 noxa Toxicity 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 238000005292 vacuum distillation Methods 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/783—CHA-type, e.g. Chabazite, LZ-218
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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Abstract
A kind of promotor of quickening synthesis CHA structure molecular sieve of the invention effectively shortens the synthesis cycle of molecular sieve, and the hydrothermal synthesis time foreshortens to 20-24h；And using above-mentioned CHA structure molecular sieve as carrier, CHA structure molecular screen base SCR catalyst is prepared by quick negative pressure impregnation method, is uniformly dispersed, without the miscellaneous peak other than CHA structure in XRD spectra；NH is carried out using simulated atmosphere on self assembly micro fixed-bed reactor3- SCR performance evaluation, operation temperature window T90(T90, NOXTemperature when conversion ratio 90%) it is 180-475 DEG C, N295% or more selectivity, average NH3Leakage rate is lower than 10ppm.
Description
Technical field
The invention belongs to Vehicular exhaust nitrogen oxides Catalytic Reducing Purification (SCR, Selective Catalytic
Reduction) technical field, a kind of fast preparation method more particularly, to CHA structure molecular sieve and leads on this basis
The method for crossing quick negative pressure impregnation preparation SCR catalyst.
Background technique
With the fast development of Domestic Automotive Industry, vehicle guaranteeding organic quantity increases year by year, and 2017 end of the year whole nations of cut-off are motor-driven
Vehicle ownership is more than 3.10 hundred million amounts, wherein 2.17 hundred million, automobile.The comprehensively universal of motor vehicle significantly improves going out for people
It goes, but has also caused a series of problems, especially pollution emission problem.According to Environmental Protection Department " Chinese automotive environment pipe
Manage annual report (2017) ", national 3419.3 ten thousand tons of motor vehicle emission pollutant carbon monoxide (CO) in 2016, hydrocarbon (HC)
422.0 ten thousand tons, nitrogen oxides (NOX) 577.8 ten thousand tons, 53.4 ten thousand tons of particulate matter (PM).By fuel grade, national emission of diesel engine
NOX70%, PM of accounting vehicle mass exhaust total quantity is then more than 90%.Therefore, exhaust gas from diesel vehicle already becomes China's atmosphere pollution
One of major source.Wherein, NOXAs one of four kinds of major pollutants, photochemical fog, acid rain, haze etc. can be caused
A series of atmosphere pollution phenomenons, seriously threaten natural environment and human health.Solve vehicle exhaust NOXPollute very urgent, mesh
Preceding SCR technology (Selective Catalytic Reduction, SCR) is most effective most widely used skill
Art.By way of additional reducing agent, under the effect of the catalyst, by NOXIt is converted to N2。
State four, five stages most widely used vanadium system SCR catalyst, due to poor performance at low temperatures, nitrogen selective it is low and
Vanadium secondary pollution problems can not be applicable in six discharge phase of state that will implement.And molecular screen base SCR catalyst will be as future
Trend has become research hotspot.CHA structure molecular sieve possesses high silica alumina ratio and small duct, frequently as the load of SCR catalyst
Body, corresponding molecular sieve catalyst have good De-NOXPerformance.Wherein, SAPO-34, SSZ-13 are automotive catalyst fields
The most common CHA structure molecular sieve carrier.Usual CHA structure molecular sieve preparation method is by silicon source, silicon source, template, alkali metal
Element etc., which sequentially adds, is prepared into complex sol, is subsequently placed in high temperature crystallizing kettle, and hydrothermal synthesis reaction is carried out under static condition,
Form molecular sieve product.This method lacks the inducer of crystal growth, and formation nucleus is slower, leads to the entire hydrothermal synthesis period
It is longer, CHA structure molecular sieve water heat generated time is synthesized in 106927474 A of patent CN to be no less than 4 days；Patent CN
CHA structure zeolite-water thermal synthesis duration 3-8 days in 107115888 A；CHA structure molecular sieve in 107282096 A of patent CN
A length of 3-7 days when hydrothermal synthesis；CHA structure zeolite-water thermal synthesis duration is 4-5 days in 106745034 A of patent CN.Separately
Outside, conventional molecular sieve hydrothermal synthesis is in static condition, for example 106745035 A of 106986354 A of patent CN and CN, in this way
The advantages of doing is to be conducive to molecular sieve growth, the disadvantage is that molecular sieve particle diameter distribution is uneven, moieties sieve size particle is larger, very
To there is caking phenomenon.
Under normal circumstances, molecular sieve SCR catalyst preparation method can be divided into infusion process and ion-exchange, and above method is negative
It carries active component and is required to drying later, often because capillary occurs for solution surface tension in duct in Jie's poromerics drying process
Coacervation causes Active components distribution uneven.In order to avoid the phenomenon, the present invention uses quick negative pressure impregnation method, using grinding
Mill processing, refines catalyst carrier particle, selects the organic matter of low boiling point low-tension as solvent, in the way of vacuum distillation
Obtain catalyst precarsor.
Summary of the invention
It is a kind of accelerate synthesis of molecular sieve method and its catalyst NH3-SCR reaction in application, it is following for solving
Problem: 1) Zeolite synthesis excessive cycle；2) catalyst activity component is unevenly distributed.
In order to solve the above technical problems, the invention the technical solution adopted is that:
A kind of promotor for accelerating synthesis CHA structure molecular sieve, the promotor is by inorganic compound promotor, organic compound
Object promotor and CHA structure molecular screen primary powder composition, inorganic compound promotor: organic compound promotor molar ratio is 1:
0.1-25, CHA structure molecular screen primary powder additional amount are every hundred milliliters of solution 0.01-0.5g.
Wherein, inorganic compound promotor is at least one in fluoride, nitrate, alkali metal salt or alkali salt
Kind, fluoride can be NH4F, one of HF, nitrate can be NH4NO3、KNO3、NaNO3、LiNO3、Mg(NO3)2In
One kind, alkali metal salt can be NaCl, Na2SO4、Na3PO4、KCl、K2SO4、K3PO4、KH2PO4One of, alkali salt
It can be MgCl2、MgSO4One of.
Wherein, organic compound promotor be tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide,
At least one of etamon chloride, triethylamine, diethylamine.
Wherein, the CHA structure molecular screen primary powder is one of SAPO-34, SSZ-13.
In addition, the present invention also resides in a kind of method for accelerating synthesis CHA structure molecular sieve with above-mentioned promotor that discloses, including
Following key step:
S1: one of sodium metaaluminate, Aluminum sol or aluminum nitrate are configured to Crystallization of Zeolite liquid, the Crystallization of Zeolite
Liquid, inorganic compound promotor, organic compound promotor and CHA structure molecular screen primary powder are proportionally mixed to form compound molten
Glue-gel.
S2: complex sol-gel in S1 is placed in reaction vessel, and synthesizes CHA structure molecule with hydrothermal synthesis method
Sieve precursor carrier；
S3: the molecular sieve carrier precursor in S2 is successively centrifuged, is washed, is dried, roasts and obtains CHA structure molecular sieve
Carrier.
Wherein, the molar ratio of promotor and aluminium element is 0.05%~5% in S1；Preferably, promotor and aluminium element
Molar ratio is 0.1~2%.
Wherein, the condition of hydrothermal synthesis method uses following ladder temperature control and program mixing control in S2, firstly, 180-200
DEG C stirring reacts 2h；Secondly, 130-160 DEG C of standing 12h；Then, it under 130-160 DEG C of constant temperature, is stirred at interval of 2h
Machine crawl 30s；
The hydrothermal synthesis method time is 20-24h.
Wherein, in S3 gained CHA structure molecular sieve carrier in without obvious stray crystal, relative crystallinity reaches 90% or more.
In addition, the present invention, which also resides in disclosure, prepares resulting CHA structure system with molecular sieve for preparing using the above method for SCR catalyst
Method, including following key step:
S1:CHA structure molecular screen support dispersion is added in water mixed alkoxide solution, macromolecule dispersing agent is added, by grinding
Grinding machine carries out grinding and homogeneous solution is made；
S2: solution with active component element is proportionally added into S1 homogeneous solution and with adjuvant component element
Solution is dispersed with stirring uniformly；
S3: S2 solution is placed in rotary evaporation bottle, and the Organic Alcohol in solution is evaporated in vacuo, obtains half-dried molecular sieve
Catalyst is made in SCR catalyst precursor, then drying roasting.
Wherein, according to mass ratio, CHA structure molecular sieve carrier: water: alcohol=1:(0.2-0.9): (1-10).
Wherein, the macromolecule dispersing agent in S1 can be (poly- for polyethylene glycol (degree of polymerization 3000-6000), polyethylene glycol
Right is 6000-10000), one of polyvinyl alcohol (degree of polymerization 6000-10000).
Wherein, active component element is loaded on the CHA structure molecular screen base in CHA structure molecular screen base SCR catalyst
And adjuvant component element, the active component element relative to carrier mass ratio be no more than 6%, the adjuvant component element relative to
The mass ratio of carrier is no more than 2.5%.
Wherein, active component element be at least one of copper, ferro element, adjuvant component element be cerium, manganese, iron, molybdenum,
At least one of selenium, niobium, lanthanum, praseodymium element.
It is being catalyzed in addition, the present invention also resides in the open CHA structure molecular screen base SCR catalyst obtained using the above method
Purify NOXIn application, specifically, in tail gas catalyzed reduction reaction (NH3- SCR) in application.
From molecular sieve crystal nucleation, growth angle is promoted, molecular screen primary powder adds technical solution provided by the invention
Enter, reduce the activation energy that nucleus is formed, organic/inorganic compound promotor improves micelle character, promotes nucleus fast-growth.Tool
Have the advantage that and the utility model has the advantages that
(1) molecular screen primary powder provides nucleus in promotor, and inorganic compound accelerates nucleus molding, guides Si-O-Al structure
It grows and molecular sieves stabilized structure, organic compound improves sol property, acceleration molecular sieve space structure is formed.Three of the above object
Texture at promotor, not only accelerate the nucleation and growth of crystal, form crystal quickly, also shorten CHA structure
The synthesis cycle of molecular sieve, hydrothermal synthesis time foreshorten to 20-24h；
(2) it using above-mentioned CHA structure molecular sieve as carrier, is catalyzed using the molecular screen base SCR of quick negative pressure impregnation method preparation
Agent avoids copper solution in micropore canals and aggregation concentration phenomena occurs since solvent volatilizees rapidly, so active specy dispersion is equal
It is even, without the miscellaneous peak other than CHA structure in XRD spectra.
(3) it is carried out on self assembly micro fixed-bed reactor using simulated atmosphere (atmospheric condition is shown in specific embodiment)
NH3- SCR performance evaluation, operation temperature window T90(T90, NOXTemperature when conversion ratio 90%) it is 180-475 DEG C, N2Selection
Property 95% or more, average NH3Leakage rate is lower than 10ppm.
Detailed description of the invention
Fig. 1 is the XRD spectra of CHA structure molecular sieve prepared by case study on implementation 1；
Fig. 2 is the NH of CHA structure molecular screen base SCR catalyst prepared by case study on implementation 13- SCR reacts NOXConversion ratio is bent
Line；
Fig. 3 is the NH of CHA structure molecular screen base SCR catalyst prepared by case study on implementation 13- SCR reacts N2Selectivity curve；
Fig. 4 is the NH of CHA structure molecular screen base SCR catalyst prepared by case study on implementation 13- SCR reacts NH3Reveal curve.
Fig. 5 is the microscopic appearance photo (SEM photograph) of CHA structure molecular sieve prepared by case study on implementation 1；
Fig. 1-Fig. 5 belongs to the result that 40-60 mesh catalyst sample is tested in self assembly micro fixed-bed reactor.
Specific embodiment
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
In the present invention, the simulated flue gas group ingredient of use: 500ppm NO, 500ppm NH3, 5%O2, N2For Balance Air,
Total flow is 1000ml/min, reaction velocity 30000h-1。
Below in conjunction with embodiment come the present invention will be described in detail create.
Case study on implementation 1
(1) preparation of molecular sieve carrier:
18.2g sodium metaaluminate is weighed first and is configured to Crystallization of Zeolite liquid, and 0.074g ammonium fluoride (NH is added thereto4F)
With 0.165g etamon chloride (TEAC) and 0.02g SAPO-34 molecular screen primary powder.It stirs evenly to form complex sol-
Gel.
Above-mentioned complex sol-gel is placed in magnetic coupling mechanic whirl-nett reaction kettle, 180 DEG C of stirrings react 2h；
150 DEG C of standing hydrothermal synthesis 12h；Then, under 150 DEG C of constant temperatures, at interval of 2h crawl blender；Blender crawl 3 times with
Afterwards, constant temperature stands hydrothermal synthesis 4h.After hydrothermal synthesis, molecular sieve precursor is successively centrifuged, washs, dry, roasting
Product is obtained, labeled as 1., Crystal Structure (XRD spectra) is shown in Fig. 1, and product occurs belonging to CHA knot as we know from the figure
The characteristic diffraction peak of structure molecular sieve illustrates molecular sieve for CHA structure.SEM photograph is shown in Fig. 5, and CHA structure point is presented in product
Son sieves unique cube pattern.Its relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
Above-mentioned 10g CHA structure molecular sieve dispersion is taken to be added to 30ml ethanol-water solution (water alcohol ratio is 45%) mixing molten
It in liquid, is added 2ml polyethylene glycol (degree of polymerization 6000-10000), carries out grinding by grinder and homogeneous solution is made；Xiang Jun
The copper nitrate solution of 2ml 49.8% is added in even solution, 0.03g cerous nitrate and 0.16g lanthanum nitrate is added as auxiliary agent, stirring
It is uniformly dispersed；Solution is placed in rotary evaporation bottle, the Organic Alcohol in solution is evaporated in vacuo, obtains half-dried molecular sieve SCR and urges
Agent precursor, then drying roasting catalyst is made, labeled as 1. -1., be catalyzed NOXThe T of conversion50(when conversion ratio is 50%
Temperature), temperature window T90(temperature range when conversion ratio >=90%) and N2Selective data is shown in Table 2, corresponding NOXConversion
Rate, N2Selectivity and NH3Amount of leakage curve is shown in Fig. 2,3,4 respectively.Fig. 2 shows the operation temperature window T of the catalyst90For 188-
475 DEG C, N2Selectivity is more than 92%, average NH3Amount of leakage is in 10ppm or less.
Case study on implementation 2
(1) preparation of molecular sieve carrier:
100g Aluminum sol (25% solid content, acid) is weighed first and is configured to Crystallization of Zeolite liquid, and 0.25g is added thereto
Potassium nitrate (KNO3) and 0.075g triethylamine (TEA) and 0.02g SAPO-34 molecular screen primary powder.Stir evenly to be formed it is compound
Sol-gel.
Above-mentioned complex sol-gel is placed in magnetic coupling mechanic whirl-nett reaction kettle, 180 DEG C of stirrings react 2h；
150 DEG C of standing hydrothermal synthesis 12h；Then, under 150 DEG C of constant temperatures, at interval of 2h crawl blender；Blender crawl 3 times with
Afterwards, constant temperature stands hydrothermal synthesis 4h.After hydrothermal synthesis, molecular sieve precursor is successively centrifuged, washs, dry, roasting
CHA structure molecular sieve is obtained, labeled as 2., relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
Above-mentioned 10g CHA structure molecular sieve dispersion is taken to be added in 30ml methanol-water (water alcohol ratio is 45%) mixed solution,
It is added 2ml polyethylene glycol (degree of polymerization 6000-10000), carries out grinding by grinder and homogeneous solution is made；To homogeneous solution
The middle copper nitrate solution that 2ml 49.8% is added is added 0.05g cerous nitrate and 0.05g manganese nitrate as auxiliary agent, is dispersed with stirring
It is even；Solution is placed in rotary evaporation bottle, the Organic Alcohol in solution is evaporated in vacuo, before obtaining half-dried molecular sieve SCR catalyst
Body, then drying roasting catalyst is made, labeled as 2. -2., be catalyzed NOXThe T of conversion50(temperature when conversion ratio is 50%
Degree), temperature window T90(temperature range when conversion ratio >=90%) and N2Selective data is shown in Table 2.
Case study on implementation 3
(1) preparation of molecular sieve carrier:
375.13g aluminum nitrate is weighed first and is configured to Crystallization of Zeolite liquid, and 4.2g potassium phosphate (K is added thereto3PO4) and
0.026g tetrabutylammonium hydroxide (TBAH) and 0.02g SAPO-34 molecular screen primary powder.It stirs evenly to form complex sol-
Gel.
Above-mentioned complex sol-gel is placed in magnetic coupling mechanic whirl-nett reaction kettle, 180 DEG C of stirrings react 2h；
150 DEG C of standing hydrothermal synthesis 12h；Then, under 150 DEG C of constant temperatures, at interval of 2h crawl blender；Blender crawl 3 times with
Afterwards, constant temperature stands hydrothermal synthesis 4h.After hydrothermal synthesis, molecular sieve precursor is successively centrifuged, washs, dry, roasting
CHA structure molecular sieve is obtained, labeled as 4., relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
Above-mentioned 10g CHA structure molecular sieve dispersion is taken to be added to 30ml ethylene glycol-water (water alcohol ratio is 45%) mixed solution
In, it is added 2ml polyethylene glycol (degree of polymerization 6000-10000), carries out grinding by grinder and homogeneous solution is made；To uniform
The copper nitrate solution of 2ml 49.8% is added in solution, 0.2g cerous nitrate is added as auxiliary agent, is dispersed with stirring uniformly；Solution is set
In rotary evaporation bottle, the Organic Alcohol in solution is evaporated in vacuo, obtains half-dried molecular sieve SCR catalyst precursor, then dries
Roasting catalyst is made, labeled as 4. -4., be catalyzed NOXThe T of conversion50(temperature when conversion ratio is 50%), temperature window T90
(temperature range when conversion ratio >=90%) and N2Selective data is shown in Table 2.
Case study on implementation 4
(1) preparation of molecular sieve carrier:
18.2g sodium metaaluminate is weighed first and is configured to Crystallization of Zeolite liquid, and 0.085g ammonium fluoride is added thereto
(NaNO3), 0.02g dipotassium hydrogen phosphate (K2HPO4) and 0.065g etamon chloride (TEAC) and 0.02g SAPO-34 points
Son sieve original powder.It stirs evenly to form complex sol-gel.
Hydrothermal synthesis step such as embodiment 1 is identical, and gained molecular sieve carrier number is that 5., relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
Above-mentioned 10g CHA structure molecular sieve dispersion is taken to be added in 30ml acetone-water (volumetric concentration 45%) mixed solution,
It is added 2ml polyvinyl alcohol (degree of polymerization 6000-10000), carries out grinding by grinder and homogeneous solution is made；To homogeneous solution
The middle copper nitrate solution that 2ml 49.8% is added is added 0.13g nitric acid niobium and 0.06g nitric acid molybdenum as auxiliary agent, is dispersed with stirring
It is even；Solution is placed in rotary evaporation bottle, the Organic Alcohol in solution is evaporated in vacuo, before obtaining half-dried molecular sieve SCR catalyst
Body, then drying roasting catalyst is made, labeled as 5. -5., be catalyzed NOXThe T of conversion50(temperature when conversion ratio is 50%
Degree), temperature window T90(temperature range when conversion ratio >=90%) and N2Selective data is shown in Table 2.
Case study on implementation 6
(1) preparation of molecular sieve carrier:
CHA structure molecular sieve feed ratio is same as Example 5.
Complex sol-gel of preparation is placed in magnetic coupling mechanic whirl-nett reaction kettle, 200 DEG C of stirring reactions
2h；155 DEG C of standing hydrothermal synthesis 12h；Then, under 155 DEG C of constant temperatures, at interval of 2h crawl blender；Blender crawl 3 times
After, constant temperature stands hydrothermal synthesis 4h.After hydrothermal synthesis, molecular sieve precursor is successively centrifuged, washs, dry, roasting
Burning obtains CHA structure molecular sieve, and for products obtained therefrom labeled as 6., relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
The molecular sieve dispersion for taking 10g made above is added in 30ml water alcohol (water alcohol ratio is 45%) mixed solution, is added
2ml polyvinyl alcohol (degree of polymerization 6000-10000) carries out grinding by grinder and homogeneous solution is made；Add into homogeneous solution
Enter the copper nitrate solution of 2ml 49.8%, 0.05g ferric nitrate and 0.05g cerous nitrate is added as auxiliary agent, is dispersed with stirring uniformly；It will
Solution is placed in rotary evaporation bottle, and the Organic Alcohol in solution is evaporated in vacuo, obtains half-dried molecular sieve SCR catalyst precursor, with
Afterwards drying roasting catalyst is made, labeled as 6. -6., be catalyzed NOXThe T of conversion50(temperature when conversion ratio is 50%), temperature
Window T90(temperature range when conversion ratio >=90%) and N2Selective data is shown in Table 2.
Case study on implementation 7
(1) preparation of molecular sieve carrier:
CHA structure molecular sieve feed ratio and molecular sieve water heat synthesis step are identical as case study on implementation 5.Obtain CHA structure point
Son sieve, labeled as 7., relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
The molecular sieve dispersion for taking 10g made above is added to 30ml methanol/ethylene glycol (molar ratio 3:1) mixed solution
In, it is added 2ml polyethylene glycol (degree of polymerization 3000-6000), carries out grinding by grinder and homogeneous solution is made；To uniformly it is molten
The copper nitrate solution of 2ml 49.8% is added in liquid, 0.1g manganese nitrate and 0.1g ferric nitrate is added as auxiliary agent, is dispersed with stirring
It is even；Solution is placed in rotary evaporation bottle, the Organic Alcohol in solution is evaporated in vacuo, before obtaining half-dried molecular sieve SCR catalyst
Body, then drying roasting catalyst is made, labeled as 7. -7., be catalyzed NOXThe T of conversion50(temperature when conversion ratio is 50%
Degree), temperature window T90(temperature range when conversion ratio >=90%) and N2Selective data is shown in Table 2.
Comparative example 1
(1) preparation of molecular sieve carrier:
82g sodium metaaluminate is weighed first and is configured to Crystallization of Zeolite liquid, does not add promotor and crystal seed.It stirs evenly to be formed
Complex sol-gel.
Above-mentioned complex sol-gel is placed in magnetic coupling mechanic whirl-nett reaction kettle, 180 DEG C of stirrings react 2h；
150 DEG C of standing hydrothermal synthesis 12h；Then, under 150 DEG C of constant temperatures, at interval of 2h crawl blender；Blender crawl 3 times with
Afterwards, constant temperature stands hydrothermal synthesis 4h.After hydrothermal synthesis, molecular sieve precursor is successively centrifuged, washs, dry, roasting
CHA structure molecular sieve is obtained, 1. labeled as DB-, relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
Above-mentioned 10g CHA structure molecular sieve dispersion is taken to be added in 30ml ethanol water (water alcohol ratio is 45%) mixed solution,
It is added 2ml polyethylene glycol (degree of polymerization 6000-10000), carries out grinding by grinder and homogeneous solution is made；To homogeneous solution
The middle copper nitrate solution that 2ml 49.8% is added, is added 0.1g cerous nitrate, is dispersed with stirring uniformly；Solution is placed in rotary evaporation bottle
In, the Organic Alcohol in solution is evaporated in vacuo, obtains half-dried molecular sieve SCR catalyst precursor, catalysis is made in then drying roasting
Agent, labeled as DB- 1. -1., be catalyzed NOXThe T of conversion50(temperature when conversion ratio is 50%), temperature window T90(conversion ratio >=
Temperature range when 90%) and N2Selective data is shown in Table 2.
Comparative example 2
(1) preparation of molecular sieve carrier:
82g sodium metaaluminate is weighed first and is configured to Crystallization of Zeolite liquid, and 0.5g potassium nitrate (KNO is added thereto3) and
0.1g tetraethyl ammonium hydroxide (TEAH) and 0.02g SAPO-34 molecular screen primary powder.Stir evenly that form complex sol-solidifying
Glue.
Above-mentioned complex sol-gel is placed in magnetic coupling mechanic whirl-nett reaction kettle, thermostatted water under 155 DEG C of static conditions
Thermal response is for 24 hours.CHA structure molecular sieve is obtained, 2. labeled as DB-, relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
Above-mentioned 10g CHA structure molecular sieve dispersion is taken to be added in 30ml alcohol-water (water alcohol ratio is 45%) mixed solution,
It is added 2ml polyethylene glycol (degree of polymerization 6000-10000), carries out grinding by grinder and homogeneous solution is made；To homogeneous solution
The middle copper nitrate solution that 2ml 49.8% is added is added 0.1 cerous nitrate as auxiliary agent, is dispersed with stirring uniformly；Solution is placed in rotation
Turn in evaporative flask, the Organic Alcohol in solution is evaporated in vacuo, obtains half-dried molecular sieve SCR catalyst precursor, then drying roasting
Catalyst is made, labeled as DB- 2. -2., be catalyzed NOXThe T of conversion50(temperature when conversion ratio is 50%), temperature window T90
(temperature range when conversion ratio >=90%) and N2Selective data is shown in Table 2.
Comparative example 3
(1) preparation of molecular sieve carrier:
Weigh 82g sodium metaaluminate first and be configured to Crystallization of Zeolite liquid, thereto be added 0.5g potassium nitrate (KNO3) and
0.1g tetraethyl ammonium hydroxide (TEAH) and 0.02g SAPO-34 molecular screen primary powder.Stir evenly that form complex sol-solidifying
Glue.
Above-mentioned complex sol-gel is placed in magnetic coupling mechanic whirl-nett reaction kettle, 180 DEG C of stirrings react 2h；
150 DEG C of standing hydrothermal synthesis 12h；Then, under 150 DEG C of constant temperatures, at interval of 2h crawl blender；Blender crawl 3 times with
Afterwards, constant temperature stands hydrothermal synthesis 4h.After hydrothermal synthesis, molecular sieve precursor is successively centrifuged, washs, dry, roasting
CHA structure molecular sieve is obtained, 3. labeled as DB-, relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
0.1g nitre is added using traditional infusion process, the copper nitrate solution of 2ml 49.8% in the molecular sieve for taking 10g made above
For sour cerium as auxiliary agent, forced air drying obtains molecular sieve SCR catalyst precursor, and catalyst is made in then drying roasting, is labeled as DB-
3. 3. catalysis NOXThe T of conversion50(temperature when conversion ratio is 50%), temperature window T90(temperature when conversion ratio >=90%
Range) and N2Selective data is shown in Table 2.
The different CHA structure molecular sieve relative crystallinity indexs of table 1
Verify embodiment
CHA structure molecular sieve catalyst screening prepared by the embodiment of the present invention 1~7 and comparative example 1~3 is prepared into 40-
60 mesh powder samples, carry out NH on the micro fixed-bed reactor of laboratory self assembly3- SCR catalytic performance test.It uses
Crystal reaction tube having a size of 15mm, loaded catalyst 2ml or so.Using simulated flue gas, composition are as follows: 500ppm NO,
500ppm NH3, 5%O2, N2For Balance Air, total flow 1000ml/min, reaction velocity 30000h-1.Catalytic performance index
T50、T90The results are shown in Table 2.
The different CHA structure molecular sieve catalyst NH of table 23- SCR performance indicator
| Sample is obvious | T50 | T90 |
| ①-① | 156℃ | 188-475℃ |
| ②-② | 153℃ | 175-470℃ |
| ③-③ | 150℃ | 190-475℃ |
| ④-④ | 149℃ | 185-470℃ |
| ⑤-⑤ | 155℃ | 180-480℃ |
| ⑥-⑤ | 148℃ | 176-465℃ |
| ⑦-⑦ | 146℃ | 175-467℃ |
| DB-①-① | 220℃ | 260-355℃ |
| DB-②-② | 213℃ | 250-400℃ |
| DB-③-③ | 175℃ | 200-455℃ |
Above an embodiment of the invention is described in detail, but the content is only the invention
Preferred embodiment should not be considered as limiting the invention the practical range of creation.It is all to be made according to the invention application range
All the changes and improvements etc., shall remain within the patent scope covered by the invention.
Claims (10)
1. a kind of promotor for accelerating synthesis CHA structure molecular sieve, which is characterized in that the promotor is promoted by inorganic compound
Agent, organic compound promotor and CHA structure molecular screen primary powder composition, inorganic compound promotor: organic compound promotor
Molar ratio is 1:0.1-25, and CHA structure molecular screen primary powder additional amount is every hundred milliliters of solution 0.01-0.5g.
2. a kind of promotor for accelerating synthesis CHA structure molecular sieve according to claim 1, which is characterized in that inorganization
Closing object promotor is at least one of fluoride, nitrate, alkali metal salt or alkali salt.
3. a kind of promotor for accelerating synthesis CHA structure molecular sieve according to claim 1, which is characterized in that organise
Conjunction object promotor be tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, etamon chloride, triethylamine,
At least one of diethylamine.
4. a kind of promotor for accelerating synthesis CHA structure molecular sieve according to claim 1, which is characterized in that the CHA
Structure molecular screen original powder is one of SAPO-34, SSZ-13.
5. a kind of method that promotor using as described in claim 1-4 is any accelerates synthesis CHA structure molecular sieve, feature
It is, including following key step:
S1: Crystallization of Zeolite liquid, inorganic compound promotor, organic compound promotor and CHA structure molecular screen primary powder are pressed
Complex sol-gel is mixed to form according to ratio.
S2: complex sol-gel in S1 is placed in reaction vessel, and molecular sieve supported with hydrothermal synthesis method synthesis CHA structure
Body precursor；
S3: the molecular sieve carrier precursor in S2 is successively centrifuged, is washed, is dried, roasts that obtain CHA structure molecular sieve supported
Body.
6. according to the method described in claim 5, it is characterized in that, the condition of hydrothermal synthesis method uses following ladder temperature control in S2
With program mixing control, firstly, 180-200 DEG C of stirring reacts 2h；Secondly, 130-160 DEG C of standing 12h；Then, 130-
Under 160 DEG C of constant temperatures, at interval of 2h blender crawl 30s；
The hydrothermal synthesis method time is 20-24h.
7. preparation method of the resulting CHA structure system with molecular sieve for preparing for SCR catalyst, feature using claim 5 the method
It is, including following key step:
S1:CHA structure molecular screen support dispersion is added in water mixed alkoxide solution, macromolecule dispersing agent is added, by grinder
It carries out grinding and homogeneous solution is made；
S2: solution with active component element is proportionally added into S1 homogeneous solution and with the molten of adjuvant component element
Liquid is dispersed with stirring uniformly；
S3: S2 solution is placed in rotary evaporation bottle, and the Organic Alcohol in solution is evaporated in vacuo, obtains half-dried molecular sieve SCR and urges
Catalyst is made in agent precursor, then drying roasting.
8. according to the method described in claim 7, it is characterized by: CHA structure in CHA structure molecular screen base SCR catalyst
Active component element and adjuvant component element are loaded on molecular screen base, the active component element relative to carrier mass ratio not
More than 6%, which is no more than 2.5% relative to the mass ratio of carrier.
9. according to the method described in claim 8, it is characterized in that, active component element be at least one of copper, ferro element,
Adjuvant component element is at least one of cerium, manganese, iron, molybdenum, selenium, niobium, lanthanum, praseodymium element.
10. the CHA structure molecular screen base SCR catalyst obtained according to 7 the method for right is in catalytic purification NOXIn application.
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