CN104220165A - 水热稳定的、低温nox 还原性nh3-scr 催化剂 - Google Patents
水热稳定的、低温nox 还原性nh3-scr 催化剂 Download PDFInfo
- Publication number
- CN104220165A CN104220165A CN201380019206.2A CN201380019206A CN104220165A CN 104220165 A CN104220165 A CN 104220165A CN 201380019206 A CN201380019206 A CN 201380019206A CN 104220165 A CN104220165 A CN 104220165A
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- China
- Prior art keywords
- metal ion
- trivalent
- catalyst
- zeolite
- catalytic converters
- Prior art date
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- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 230000009467 reduction Effects 0.000 title description 2
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 116
- 239000010457 zeolite Substances 0.000 claims abstract description 78
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 76
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 76
- 230000003197 catalytic effect Effects 0.000 claims abstract description 33
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 9
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical group O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 23
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 17
- 150000002602 lanthanoids Chemical class 0.000 claims description 17
- 241000264877 Hippospongia communis Species 0.000 claims description 13
- MFGOTAHWOBKNNU-XMHGGMMESA-N Isodigeranyl Chemical group CC(C)=CCC\C(C)=C\CC(C)(C=C)CCC=C(C)C MFGOTAHWOBKNNU-XMHGGMMESA-N 0.000 claims description 7
- MFGOTAHWOBKNNU-FQEVSTJZSA-N Isodigeranyl Natural products CC(=CCCC(=CC[C@](C)(CCC=C(C)C)C=C)C)C MFGOTAHWOBKNNU-FQEVSTJZSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011819 refractory material Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims 2
- 239000000203 mixture Substances 0.000 abstract description 9
- 230000007423 decrease Effects 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 35
- 229910021529 ammonia Inorganic materials 0.000 description 17
- 239000010949 copper Substances 0.000 description 14
- 239000002912 waste gas Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- -1 RTE Chemical compound 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 206010058490 Hyperoxia Diseases 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- PWOSZCQLSAMRQW-UHFFFAOYSA-N beryllium(2+) Chemical compound [Be+2] PWOSZCQLSAMRQW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910021641 deionized water Inorganic materials 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
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000222 hyperoxic effect Effects 0.000 description 1
- 229910001449 indium ion Inorganic materials 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- YOWAEZWWQFSEJD-UHFFFAOYSA-N quinoxalin-2-amine Chemical compound C1=CC=CC2=NC(N)=CN=C21 YOWAEZWWQFSEJD-UHFFFAOYSA-N 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910001419 rubidium ion Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZOKXUAHZSKEQSS-UHFFFAOYSA-N tribufos Chemical compound CCCCSP(=O)(SCCCC)SCCCC ZOKXUAHZSKEQSS-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 229910052725 zinc 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
- 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
-
- 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
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- 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
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
-
- 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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
-
- 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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/068—Noble metals
-
- 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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- 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
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Abstract
催化剂组合物包括异双金属沸石,其特征在于负载有铜离子和至少一种除Al3+之外的三价金属离子的菱沸石结构。该催化剂组合物减少了柴油废气中的NOx排放并且适合在催化转化器中运行。
Description
相关申请的交叉引用
本申请要求于2012年2月24日提交的美国申请第13/404,071号的优先权权益,其通过参考的方式全部引入本文。具体参考的是于2010年8月13日提交的美国专利申请第12/855,794号,2012年2月16日公开的公开号20120039759,标题为“基于沸石的SCR催化剂及其在柴油发动机排放处理中的用途”,Chaitanya K.Narula和Xiaofan Yang,其全部内容通过参考的方式引入本文。
根据美国能源部和UT-Battelle,LLC之间的合同号DE-AC05-00OR22725,美国政府享有本发明中的权利。
背景技术
已知柴油发动机比它们的汽油对应物(counterpart)显著更省油。因此,在公路和越野系统(例如,工业或家用设备,如重型机械和割草机)中采用柴油发动机是非常可取的。此外,在富氧环境下运行的汽油发动机(贫汽油发动机)也比目前使用的化学计量发动机(stoichiometric engines)更省油。
柴油发动机和贫汽油发动机(lean gasoline engines)的高燃油效率产生主要含有NOx气体的富氧(即“贫”)废气。虽然从(如汽油发动机排放所产生的)缺氧废气中可有效去除NOx气体,但从柴油/贫汽油发动机的贫排放物(leanemissions continues)中去除NOx气体仍然是重大挑战。特别是,标准的三元催化剂非常适用于汽油发动机,但当其被用于柴油发动机时不能满足EPA法规要求。
为了满足针对柴油发动机的EPA法规要求,正在广泛努力寻找可有效处理柴油发动机排出的富氧排放物中的NOx的催化剂。减少柴油排放物中NOx的主要方法是选择性催化还原(SCR)。在SCR中,氨或尿素通常用作还原剂。用于在柴油发动机排放的贫环境下还原NOx的最知名的NH3-SCR催化剂为Cu-ZSM-5和Fe-ZSM-5。已证明这些催化剂只有在窄的温度范围内才能有效地发挥作用。Cu-ZSM-5通常在较低的温度下表现出较好的NOx还原活性,而Fe-ZSM-5在较高的温度下表现出较好的活性。因此,Cu-ZSM-5和Fe-ZSM-5沸石的组合(即作为非均相混合物)已被试图用来在拓宽的温度范围内有效地处理NOx。最新一代NH3-SCR催化剂基于Cu-SSZ-13且现在是市售的。
虽然Cu/Fe混合物改进了柴油运行的客运车辆的排放处理,但是Cu/Fe混合物在低温下是明显不足的。特别是,目前使用的催化剂在低温(例如150-200℃)下不能有效地减少NOx排放,而这在越野柴油发动机中比客运车辆更为重要。此外,Cu/Fe混合物可能仅在单独的窄温度范围(例如,高和低的温度范围)内是足够有效的。然而,特别对于可在宽的温度范围内运行的越野柴油发动机而言,可较宽的温度范围(例如150℃至650℃)有效运行的催化剂具有显著的好处。如果汽油发动机在贫模式下运行,那么在低温下不会产生很多NOx。然而,本发明中所述的催化剂适用于在贫模式下运行的汽油发动机以及用于运输的柴油发动机(汽车、卡车、火车发动机、船舶等)。
发明概述
根据本发明的实施例,本发明的上述和其它目的通过包括异双金属沸石的催化剂组合物来实现,该异双金属沸石(heterobimetallic zeolite)的特征在于负载有铜离子和至少一种除Al3+之外的三价金属离子的菱沸石结构。该催化剂组合物降低柴油废气中的NOx排放并适合于在催化转化器中运行。
附图说明
图1为显示根据本发明的实施例的CuFe-SSZ-13和Cu-SSZ-13催化剂的性能比较的图表。
图2为显示根据本发明的实施例的CuFe-SSZ-13和经老化的CuFe-SSZ-13催化剂的性能比较的图表。
为了更好地理解本发明及其其它和进一步的目的、优点和能力,结合上述附图参考以下公开内容和所附的权利要求书。
具体实施方式
本发明涉及一种用于减轻(即去除或减少)来自烃(例如,柴油、汽油和/或煤油废气)的NOx排放的催化剂。所述催化剂包括一类新的基于菱沸石结构的异双金属沸石,例如CuFe-SSZ-13。本文所述的新沸石克服了用于NOx还原的所有已知NH3-SCR催化剂的水热耐久性问题,同时保持其在低温下的高NOx还原能力。
本文所考虑的沸石可以是任何在高温条件下(即至少100℃、150℃、200℃、250℃、300℃以及高达例如,500℃、550℃、600℃、650℃、700℃、750℃、800℃、850℃或900℃的更高的温度)稳定的本领域已知的多孔硅铝酸盐结构。在本发明的具体实施例中,沸石从至少100℃至高达700℃是稳定的。通常,沸石因具有结晶结构或部分结晶结构而有序。沸石通常可被描述为包含通过共享氧原子而互相连接的(即交联的)硅酸盐(SiO2或SiO4)和铝酸盐(Al2O3或AlO4)单元的三维骨架(framework)。
沸石可以是微孔的(即孔径小于2μm)、介孔的(即,孔径在2-50μm内,或其中的子区间(sub-range)内)或它们的组合。在本发明的几个实施例中,沸石材料完全或基本是微孔的。通过完全或基本是微孔的,源自微孔的孔体积可以为,例如,100%,或至少95%、96%、97%、98%、99%或99.5%,剩余的孔体积源自介孔,或在本发明的一些实施例中,源自大孔(孔径大于50μm)。在本发明的其它实施例中,沸石材料完全或基本是介孔的。通过完全或基本是介孔的,源自介孔的孔体积可以为,例如,100%或至少为95%、96%、97%、98%、99%或99.5%,剩余的孔体积源自微孔,或在本发明的一些实施例中,源自大孔。在本发明的另外其它实施例中,沸石材料同时包含大量微孔和介孔。通过同时包含大量的微孔和介孔,源自介孔的孔体积可以为,例如高达、至少为或精确至50%、60%、70%、80%或90%,剩余的孔体积源自微孔,或反之亦然。
各种形式的沸石通过各自的缩写而通常已知,例如ABW、ACO、AEI、AEN、AFG、AFN、AFT、AFX、APC、APD、ATN、ATT、ATV、AWO、AWW、BCT、BIK、BOF、BRE、CAS、CDO、CHA、DFT、DOH、EAB、EPI、ERI、ESV、FAR、FRA、GIS、GIU、IHW、ITE、ITW、JBW、JRY、KFI、LAU、LEV、LIO、LOS、LTA、LTN、MAR、MON、MTF、MWW、NAT、NSI、OWE、PAU、PHI、RHO、RTE、RTH、RWR、SAS、SAT、SAV、SBN、SIV、SOD、STI、STT、THO、TOL、UEI、UFI或ZON。沸石的一些具体实例包括菱沸石类沸石(例如,SSZ-13、SSZ-62、Phi、SAPO-34、LZ-218和Linde D)。菱沸石类沸石的组成、结构和性质是本领域公知的,并且已经被详细地描述,例如可在美国专利4,544,538、6,709,644、4,124,686、4,333,859和2,950,952中找到,其内容以参考的方式全部引入本文。
沸石可具有任何合适的二氧化硅-氧化铝比(即SiO2/Al2O3或“Si/Al”)。例如,在本发明的多个实施例中,沸石可具有精确地、至少、少于或高达1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、20、25、30、35、40、45、50、55、60、65、70、75、80、85、90、95、100、120、150或200的Si/Al比,或在以任意两个上述值为界的范围内的Si/Al比。在本发明的具体实施例中,沸石具有1-45的Si/Al比。
在本发明的具体实施例中,沸石为SSZ-13,其属于ABC-6族的沸石,所有的这些ABC-6族沸石也被考虑在内。在本发明的具体实施例中,SSZ-13沸石以式RNaNabAl2.4Si33.6O72·wH2O(1.4<a<27)(0.7<b<4.3)(1<w<7)表示,其中RN为N,N,N-1-三甲基金刚烷铵(trimethyladamantammonium)。
通常,沸石包含一定含量的阳离子物质(cationic species)。如本领域公知的,阳离子物质的含量通常与沸石中的铝含量成比例。这是因为用化学价较低的铝原子取代硅原子需要抗衡阳离子(countercation)的存在以建立电荷平衡。阳离子物质的一些实例包括氢离子(H+)、碱金属离子、碱土金属离子和主族金属离子。在沸石中可包含的碱金属离子的一些实例包括锂离子(Li+)、钠离子(Na+)、钾离子(K+)、铷离子(Rb+)和铯离子(Cs+)。在沸石中可包含的碱土金属离子的一些实例包括铍离子(Be2+)、镁离子(Mg2+)、钙离子(Ca2+)、锶离子(Sr2+)和钡离子(Ba2+)。在沸石中可包含的主族金属离子的一些实例包括硼离子(B3+)、镓离子(Ga3+)、铟离子(In3+)和砷离子(As3+)。在本发明的一些实施例中包括阳离子物质的组合。阳离子物质可以是微量的(例如,不超过0.01%或0.001%),或任选大量的(例如,0.01%以上,以及高达例如沸石的0.1重量%、0.5重量%、1重量%、2重量%、3重量%、4重量%或5重量%)。
上述沸石负载有一定含量的铜离子。铜离子本质上可以是一价铜(Cu+)或二价铜(Cu2+)。铜负载量可以为任意适合的量。在本发明的不同实施例中,铜负载量为,精确为、至少为、少于或高达,例如,0.01%、0.02%、0.03%、0.04%、0.05%、0.06%、0.07%、0.08%、0.09%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2.0%、2.1%、2.2%、2.3%、2.4%或2.5%,或铜负载量在以任意两个上述值为界的范围内,其中负载量表示为以沸石重量计的金属含量。在本发明的具体实施例中,铜负载量为高达2.5%的任意值。
除铜离子之外,本发明的沸石催化剂还包括至少一种三价金属离子。如本文所使用的,术语“三价金属离子”定义为除铝离子(Al3+)之外的三价金属离子。不希望受限于任何理论,认为三价金属被引入至沸石材料中。因此,认为引入的三价金属离子在沸石中与合适数量的氧原子键合,即,作为紧密接近(例如在电子接触或传递的范围内(within electronic contact orcommunication))铜离子的金属氧化物单元。据认为三价金属离子与铜离子之间的紧密接近导致不同于当它们未如此紧密接近时的这些离子的累积效应的组合效应。本文主要考虑的效应是对所得的催化剂处理NOx气体的能力(即催化剂的NOx转化能力)的效应。
在本发明的一些实施例中,除铝离子之外只有一种类型的三价金属离子被引入沸石。在本发明的其它实施例中,除铝离子之外至少两种类型的三价金属离子被引入沸石。在本发明的另外其它实施例中,除铝离子之外至少三种类型的三价金属离子被引入沸石。在本发明的另外其它实施例中,确切地,除铝离子之外的两种或三种类型的三价金属离子被引入沸石。
可以以任意合适的量将三价金属离子中的每一种包含在内,例如,精确为、至少为、少于或高达,例如0.01%、0.02%、0.03%、0.04%、0.05%、0.06%、0.07%、0.08%、0.09%、1.0%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2.0%、2.1%、2.2%、2.3%、2.4%或2.5%,或含量在以任意两个上述值为界的范围内。在本发明的具体实施例中,可以精确为、至少为、少于或高达2.5%的量将每个三价金属离子包含在内,。在本发明的实施例中,其中包括不止一种类型的三价金属离子,每种金属的负载量可独立地选自任何上述示例性的量或其中的范围。在本发明的其它实施例中,除铝之外的三价金属离子的总量与以上提供的任何示例性的值一致。
在本发明的第一组实施例中,至少一种三价金属离子选自三价的过渡金属离子。一种或多种过渡金属可以选自下述类型的过渡金属的任意部分或选定部分:元素周期表中的第IIIB族(Sc族)、第IVB族(Ti族)、第VB族(V族)、第VIB族(Cr族)、第VIIB族(Mn族)、第VIIIB族(Fe和Co族)的元素。三价过渡金属离子的一些实例包括Sc3+、Y3+、V3+、Nb3+、Cr3+、Fe3+和Co3+。在本发明的其它实施例中,三价金属离子排除全部过渡金属离子,或任选地,排除上述给出的任意一种、两种或多种类别的过渡金属离子或其具体实例。在本发明的具体实施例中,三价过渡金属离子包括Sc3+或Fe3+,或它们的组合。
在本发明的第二组实施例中,至少一种三价金属离子选自三价主族金属离子。一种或多种主族金属可以选自除铝之外周期表中第IIIA族(B族)和/或第VA族(N族)元素中的任一部分或选定部分。三价主族金属离子的一些实例包括Ga3+、In3+、As3+、Sb3+和Bi3+。在本发明的其它实施例中,三价金属离子排除除铝离子之外的全部主族金属离子,或任选地,排除上述给出的任意一种、两种或多种类别的主族金属离子或其具体实例。在本发明的具体实施例中,三价主族金属离子包括至少In3+。
在本发明的第三组实施例中,至少一种三价金属离子选自三价镧系金属离子。本文所考虑的三价镧系金属离子的一些实例包括La3+、Ce3+、Pr3+、Nd3+、Sm3+、Eu3+、Gd3+、Tb3+、Dy3+、Ho3+、Er3+、Tm3+、Yb3+和Lu3+。在本发明的具体实施例中,三价镧系金属离子选自La3+、Ce3+、Pr3+和Nd3+中的一种或其组合。在本发明的其它具体实施例中,三价镧系金属离子为或包括La3+。
在本发明的第四组实施例中,至少两种三价金属离子选自三价过渡金属离子。本文所考虑的三价过渡金属离子的一些组合包括Sc3+和一种或多种其它三价过渡金属离子的组合,或Fe3+和一种或多种其它三价过渡金属离子的组合,或Y3+和一种或多种其它三价过渡金属离子的组合。
在本发明的第五组实施例中,至少两种三价金属离子选自三价主族金属离子。本文所考虑的三价主族金属离子的一些组合包括In3+和一种或多种其它三价主族金属离子的组合,或Ga3+和一种或多种其它三价主族金属离子的组合,或As3+和一种或多种其它三价主族金属离子的组合。
在本发明的第六组实施例中,至少两种三价金属离子选自三价镧系金属离子。本文所考虑的三价镧系金属离子的一些组合包括La3+和一种或多种其它三价镧系金属离子的组合,或Ce3+和一种或多种其它三价镧系金属离子的组合,或Pr3+和一种或多种其它三价镧系金属离子的组合,或Nd3+和一种或多种其它三价镧系金属离子的组合。
在本发明的第七组实施例中,至少一种三价金属离子为三价过渡金属离子且至少一种三价金属离子为三价镧系金属离子。例如,在本发明的具体实施例中,至少一种三价金属离子选自Sc3+、Fe3+和/或Y3+,而另一种三价金属离子选自La3+、Ce3+、Pr3+和/或Nd3+。
在本发明的第八组实施例中,至少一种三价金属离子为三价过渡金属离子且至少一种三价金属离子为三价主族金属离子。例如,在本发明的具体实施例中,至少一种三价金属离子选自Sc3+、Fe3+和/或Y3+,而另一种三价金属离子选自In3+、Ga3+和/或In3+。
在本发明的第九组实施例中,至少一种三价金属离子为三价主族金属离子且至少一种三价金属离子为三价镧系金属离子。例如,在本发明的具体实施例中,至少一种三价金属离子选自Sc3+、Fe3+和/或Y3+,而另一种三价金属离子选自La3+、Ce3+、Pr3+和/或Nd3+。
在本发明的第十组实施例中,至少三种三价金属离子被包含在沸石中。至少三种三价金属离子可以选自三价过渡金属离子、三价主族金属离子和/或三价镧系金属离子。
在本发明的具体实施例中,一种、两种、三种或更多种三价金属离子选自Sc3+、Fe3+、Y3+、La3+、Ce3+、Pr3+、Nd3+、In3+和/或Ga3+。在本发明的更具体实施例中,一种、两种、三种或更多种三价金属离子选自Sc3+、Fe3+、La3+和/或In3+。
上述沸石催化剂通常没有涂覆包含金属的膜或层。然而,如本文所期望的,只要膜或层基本上不阻碍催化剂作为NOx还原催化剂有效地起作用,本发明也会考虑涂覆有包含金属的膜或层的上述沸石催化剂。通过涂覆,膜或层存在于沸石的表面上。在本发明的一些实施例中,沸石的表面只表示外表面(即,由沸石催化剂外轮廓面积所限定的),而在本发明的其它实施例中,沸石的表面表示或包括沸石的内表面,例如沸石的孔隙或孔道内的表面。包含金属的膜或层可以用于,例如,调整催化剂的物理特性、催化效率或催化选择性。包含金属的表面的一些实例包括碱金属、碱土金属和二价过渡或主族金属(例如,Zn2+、Fe2+、Co2+、Ni2+、Pd2+、Pt2+、Sn2+或Pb2+)、四价过渡金属(例如,Ti4+、Zr4+、Rh4+、Ir4+、Mn4+、Ge4+、Sn4+和Te4+)、五价过渡或主族金属(例如,Nb5+、Ta5+和Sb5+)和六价过渡金属(例如,Cr6+、Mo6+和W6+)的氧化物和/或硫化物。在本发明的其它实施例中,将一种多种类别或具体类型的任意上述额外金属离子从沸石催化剂中排除。
本文所述的催化剂可通过本领域已知的任何合适方法来合成。本文所考虑的方法应将金属离子(即,铜和一种或多种三价金属离子)均匀地引入沸石中。所得到的负载有金属的催化剂含有在分子水平上均匀分布的金属离子,即,催化剂不包含仅含一种类型的金属离子的宏观区域,如通过研磨和混合各自含有不同金属离子的两种沸石源来获得。
在本发明的具体实施例中,本文所述的催化剂首先通过用待负载的金属浸渍沸石来制备。浸渍步骤可例如通过用一种或多种包含待负载的金属的溶液处理沸石来实现。通过用包含金属的溶液处理沸石,使包含金属的溶液与沸石接触,使得溶液被吸收进沸石中,优选被吸收进全部体积的沸石中。
在一个实施方式中,浸渍步骤通过用包含待负载的全部金属的溶液处理沸石来实现。在另一个实施方式中,浸渍步骤通过用两种或更多种溶液处理沸石来实现,其中不同溶液包含不同金属或金属组合。用浸渍溶液对沸石的每一次处理对应于一个单独的浸渍步骤。通常,当采用多于一个的浸渍步骤时,在浸渍步骤之间采用干燥和/或热处理步骤。
金属浸渍溶液包含至少一种或多种待负载入沸石的金属离子,以及用于将金属离子分散入沸石的液体载体。金属离子通常为金属盐的形式。优选地,金属盐完全溶解于液体载体。金属盐包含与一种或多种抗衡阴离子(counteranion)呈离子键合的金属离子。上述的任意一种或多种金属离子可以充当金属离子部分。抗衡阴离子可以选自,例如,卤素(F-、Cl-、Br-或I-)、羧酸根(例如,甲酸根、乙酸根、丙酸根或丁酸根)、硫酸根、硝酸根、磷酸根、氯酸根、溴酸跟、碘酸根、氢氧根、β-二酮酸根(β-diketonate)(例如乙酰丙酮酸根(acetylacetonate))和二羧酸根(例如,草酸根、丙二酸根或丁二酸根)。在本发明的一些实施例中,抗衡阴离子可含有一种或多种金属,包括负载入沸石中的一种或多种金属。此类抗衡阴离子的一些实例包括钛酸根、锆酸根、钒酸根、铌酸根、钽酸根、铬酸根、钼酸根、钨酸根、砷酸根、锑酸根、锡酸根和碲酸根。在本发明的其它实施例中,将一种或多种类别或具体类型的任意上述抗衡阴离子从浸渍溶液中排除(或任选地,从被引入沸石的溶液中排除)。
在本发明的具体实施例中,催化剂通过形成包含沸石粉末和待引入的金属的浆料(slurry)来制备。干燥和烧制(fire)所得浆料以形成粉末。然后粉末和有机和/或无机粘合剂结合并对其进行湿混合以形成糊料(paste)。所得到的糊料可以形成任意希望的形状,例如,通过挤出形成棒状、蜂巢状或针轮状(pinwheel)结构。然后将经挤出的结构干燥和烧制以形成最终的催化剂。在本发明的其它实施例中,将沸石粉末、金属和粘合剂全部结合在一起以形成糊料,然后将其挤压和烧制。
浸渍沸石后,通常将负载有金属的沸石干燥和/或经历热处理步骤(例如,烧制或煅烧步骤)。热处理步骤起到将经浸渍的金属永久地引入沸石的作用,例如,通过在沸石材料中形成金属氧化物键。在本发明的不同实施例中,在至少100℃、150℃、200℃、250℃、300℃、350℃、400℃、450℃、500℃、550℃、600℃、650℃、700℃、750℃或800℃的温度或其中范围内的温度下,可以实施热处理步骤一时间段,例如,15分钟、30分钟、1小时、2小时、6小时、12小时、24小时、30小时、36小时或48小时,或其中范围内的时间段。在本发明的具体实施例中,热处理步骤在至少500℃的温度下实施至少两个小时的时间段。在本发明的一些实施例中,热处理步骤包括从较低温度到较高温度和/或从较高温度到较低温度的温度斜坡(ramping)步骤。例如,热处理步骤可以包括以1、2、5或10℃/min的速率从100℃至700℃的斜坡段,反之亦然。
通常,在正常的环境压力下实施一个或多个热处理步骤。然而,在本发明的一些实施例中,采用高压(例如,高于1atm且高达2、5或10atm),而在本发明的其它实施例中,采用低压(例如,低于1、0.5或0.2atm)。此外,虽然通常在正常大气环境下实施热处理步骤,但在本发明的一些实施例中,使用高氧、减低氧或惰性气氛。在处理气氛中可包含的一些气体包括,例如,氧气、氮气、氦气、氩气、二氧化碳和它们的混合物。
通常,本文所述的沸石催化剂是粉末的形式。在本发明的第一组实施例中,至少部分的或全部的粉末颗粒具有小于微米的尺寸(即,纳米级颗粒)。纳米级颗粒可以具有精确为、至少为、高达或小于,例如,1、2、5、10、20、30、40、50、60、70、80、90、100、150、200、250、300、350、400、450、500、550、600、650、700、750、800、850、900或950纳米(nm)的颗粒尺寸,或在以任意两个上述值为界的范围内的颗粒尺寸。在本发明的第二组实施例中,至少部分或全部粉末状颗粒具有等于或高于1微米的尺寸。微米级的颗粒可以具有精确为、至少为、高达或小于,例如,1、2、5、10、20、30、40、50、60、70、80、90或100微米(μm)的颗粒尺寸,或在以任意两个上述值为界的范围内的颗粒尺寸。在本发明的一些实施例中,催化剂的单晶或晶粒对应于上述提供的任意尺寸,而在本发明的其它实施例中,催化剂的晶体或晶粒聚结以提供具有任意上述示例性尺寸的经聚结的晶体或晶粒。
在本发明的其它实施例中,沸石催化剂可以为膜、涂层或多层膜或涂层的形式。涂层或多重涂层的厚度可以为,例如,1、2、5、10、50或100微米,或其中的范围,或高达100微米的厚度。在本发明的另外其它实施例中,沸石催化剂是非颗粒(即连续的)块状固体的形式。在本发明的另外其它实施例中,沸石催化剂可以是纤维的或网格(mesh)的形式。
催化剂还可以与适用于在催化转化器中工作的载体材料混合或附着于所述适用于在催化转化器中工作的载体材料。载体材料可以是(例如具有任意上述的颗粒尺寸的)粉末,(例如0.5mm或颗粒尺寸更大的)颗粒,块状材料,例如流入型蜂巢状单块(a honeycomb monolith of the flow-through type)、板状或多板状结构或波纹状金属片(corrugated metal sheets)。如果使用蜂巢状结构,蜂巢状结构可以包含任意合适的蜂房(cell)密度。例如,蜂巢状结构可以每平方英尺具有100、200、300、400、500、600、700、800或900个蜂房(蜂房/平方英尺)(或62-140蜂房/平方厘米)或更大。载体材料通常由耐火材料组合物构成,例如那些包含堇青石、莫来石、氧化铝(例如,α-、γ-或θ-氧化铝)或氧化锆,或它们的组合的组合物。特别地,蜂巢状结构被详细描述于,例如美国专利5,314,665、7,442,425和7,438,868中,其内容通过参考的方式全部引入本文。当使用波纹状的或其它类型的金属片时,这些金属片可以在彼此的其上载有催化剂材料的顶部层叠,从而保留了能使废气在这些片材之间流动的通道。通过弯曲这些片材也可以使这些层状的片材形成例如圆筒状结构。
本文所述的催化剂优选呈现NOx转化温度分布(conversion temperatureprofile),其比例如美国专利7,601,662中所述的Cu-SSZ-13的分布有所改进。
在本发明的第一组实施例中,本文所述的催化剂优选在150℃时呈现出高的NOx转化率。如本文中所使用的,短语“在150℃时的高NOx转化率”定义为在150℃时至少或高于50%、55%、60%、65%、70%、75%、80%或85%的NOx转化率。
在本发明的第二组实施例中,本文所述的催化剂优选在200℃时呈现出高的NOx转化率。如本文中所使用的,短语“在200℃时的高NOx转化率”定义为在200℃时至少或高于80%、85%或90%的NOx转化率。
在本发明的第三组实施例中,本文所述的催化剂优选在250℃至450℃的温度范围内呈现出高的NOx转化率。如本文中所使用的,短语“在250-450℃时高NOx转化率”定义为在250℃、300℃、350℃、400℃或450℃的温度下,在250℃至450℃的温度范围内,或在此范围内变化的温度下,至少或高于60%、65%、70%、75%、80%、85%或90%的NOx转化率。
在本发明的第四组实施例中,本文所述的催化剂优选在500℃至525℃的温度范围内呈现出高的NOx转化率。如本文中所使用的,短语“在500-525℃时的高NOx转化率”定义为在500℃至525℃的温度范围内,或在此范围内变化的温度下,至少或高于60%、65%、70%、75%、80%或85%的NOx转化率。
在本发明的第五组实施例中,本文所述的催化剂优选在550℃的温度时呈现出高的NOx转化率。如本文中所使用的,短语“在550℃时的高NOx转化率”定义为在550℃的温度下至少或高于60%、65%、70%、75%或80%的NOx转化率。
在本发明的第六组实施例中,本文所述的催化剂优选在600℃至650℃的温度范围内呈现出高的NOx转化率。如本文中所使用的,短语“在600-650℃时的高NOx转化率”定义为在600℃至650℃的温度范围内,或在此范围内变化的温度下,至少或高于60%、65%、70%、75%或80%的NOx转化率。
在本发明的第七组实施例中,本文所述的催化剂优选在150℃时呈现出高的NOx转化率,同时也在200℃时呈现出高的NOx转化率,和/或在250-450℃时呈现出高的NOx转化率,和/或在500-525℃时呈现出高的NOx转化率,和/或在550℃时呈现出高的NOx转化率,和/或在600-650℃时呈现出高的NOx转化率。
在一些实施例中,本发明涉及其中含有作为催化剂的上述负载有金属的沸石催化剂的催化转化器。催化剂通常置于耐火材料的支撑元件上,例如波纹状金属片或蜂巢状结构,如上所述。催化转化器可以是本领域已知的任何催化转化器,且具体为那些特别适合于处理柴油废气的催化转化器。此类催化转化器的构造和操作是本领域公知的,正如在,例如,美国专利7,691,340、7,678,348、7,575,727、7,442,425、7,438,868、7,412,824、7,288,230、6,919,052和5,314,665中所详细描述的,其内容通过参考的方式全部引入本文。
作为基础元件,催化转化器通常含有置于支撑元件上的催化剂,以便于通道可使得废气穿过其中并将所负载的催化剂封闭在金属外壳中。金属外壳通常与一个或多个进气口(即管道)相连以将废气传送至所负载的催化剂。金属外壳也可以包括一个或多个垫片。
在本发明的具体实施例中,催化转化器与氨源相连,以便氨与废气流相混合。如本领域公知的,氨用作选择性催化还原(SCR)过程中的还原剂。氨可以是任何合适的形式,例如无水氨、氨水、尿素、碳酸铵、甲酸铵或氨基甲酸铵。在本发明的一些实施例中,可在废气流到达催化剂之前和/或期间将氨源连续地供给到废气流中。在本发明的其它实施例中,间歇性地供氨。在本发明的其它实施例中,在废气流到达催化剂之前供给氨源。在这种方式中,氨源在与废气流反应之前被首先吸收进催化剂中。通常,使用氨储存罐来容纳氨源。
在设计SCR系统时,大量的其它元件可与催化转化器和氨源连接。例如,在氨源和催化转化器之间可包括蒸发器以将氨源转换(即分解)为氨气。在氨源和催化转化器之间(或在蒸发器和催化转化器之间)也可引入混合器以将氨与废气流混合。可包括其它元件,例如加热器、泵和风扇,以优化该系统。SCR系统可集成到使用稀燃发动机(lean burn engine)的任何系统中,特别是那些使用柴油燃料的发动机。SCR系统可集成到,例如客车、卡车、电站锅炉、工业锅炉、固体垃圾锅炉(即,如在城市垃圾的处理中所用的)、船舶、机车、隧道掘进机、潜艇、建筑设备、燃气涡轮机、发电机、飞机、割草机或链锯的发动机系统中。
下面列出了用于解释本发明目的和描述本发明一些具体实施例的实施例。然而,本发明的范围不希望以任何方式受限于本文所列出的实施例。
实施例I
根据美国专利4,544,538制备H-SSZ-13。如下合成Cu-SSZ-13:将2.664g Cu(OAc)2·H2O样品溶于600mL去离子水(0.022M)中,然后加入H-SSZ-13(10.00 g)。将浆料在50℃的温度下搅拌2小时。冷却后通过过滤收集蓝色固体,用去离子水清洗,并在500℃(10℃/min)的温度下在空气中煅烧4小时,从而得到Cu-SSZ-13。元素分析:Cu 3.46,Al 4.05%。
CuFe-SSZ-13通过以下方法获得:将10g Cu-SSZ-13悬浮于50mL0.015M Fe(NO3)3的水溶液中,用N2除气,并在80℃的温度下持续搅拌2小时。过滤后获得黄色固体,且滤液为无色透明的。然后将产物在500℃(2℃/min)的温度下于空气中煅烧2小时,从而得到浅黄色CuFe-SSZ-13。元素分析:Cu 2.71%,Fe 0.357%,Al 3.86%。
CuFe-SSZ-13也可通过初湿含浸法(incipient wetness method)来制备。在该方法中,将10g Cu-SSZ-13与0.3 g Fe(NO3)3.9H2O一起研磨并加入刚好足够覆盖Cu-SSZ-13表面的水。Cu-SSZ-13的颜色缓慢地从绿色变为黄色。使样品在空气中干燥,然后在500℃(2C/min)的温度下在空气中煅烧4小时,从而得到浅黄色CuFe-SSZ-13。
实施例II
对Cu-SSZ-13和CuFe-SSZ-13催化剂粉末进行比较试验。将催化剂粉末与等量(以重量计)惰性堇青石混合并转移到台式反应器。在8.5%O2、8%CO2和7.25%H2O和差额(balance)N2的气流中、于600℃(进气温度)的温度下、以50,000 h-1的空速脱绿(de-green)两小时。NOx转化效率实验采用在50,000h-1的空速下的含8.5%O2、8%CO2、7.25%H2O、250 ppm NO2、250 ppm NO、500 ppm NH3和作为差额的N2的模拟柴油废气并在150℃至650℃的温度范围内进行评价。结果示于图1中。CuFe-SSZ-13催化剂在150-650℃的范围内清楚地显示出更好的性能。NOx转化性能差异在150℃时尤其明显,其中在试验条件下Cu-SSZ-13转化40%的NOx,而CuFe-SSZ-13转化~75%的NOx。
实施例III
通过采用老化方案在CuFe-SSZ-13催化剂粉末上进行加速老化,所述老化方案为在含有10%水的空气流下将催化剂暴露于675℃的温度50小时。测试结果示于图2中。
CuFe-SSZ-13催化剂在150-650℃的范围内显示出高的水热耐久性和高的NOx转化性能。150℃时NOx还原量(NOx reduction)为~65%,其优于新鲜的Cu-SSZ-13,如图1所示。
尽管已经显示和描述了目前所认为的本发明的实施例,但对于本领域技术人员而言显而易见的是,可在不脱离所附的权利要求书所限定的本发明范围的情况下进行各种改变和修改。
Claims (31)
1.催化剂组合物,其包含异双金属沸石,所述异双金属沸石的特征在于负载有铜离子和至少一种除Al3+之外的三价金属离子的菱沸石结构,且其中所述催化剂组合物减少柴油废气中的NOx排放。
2.根据权利要求1的催化剂,其中所述至少一种三价金属离子包括三价过渡金属离子。
3.根据权利要求2的催化剂,其中所述至少一种三价过渡金属离子选自Sc3+、Y3+、V3+、Nb3+、Cr3+、Fe3+和Co3+。
4.根据权利要求1的催化剂,其中所述至少一种三价金属离子包括三价主族金属离子。
5.根据权利要求4的催化剂,其中所述三价主族金属离子选自Ga3+、In3+、As3+、Sb3+和Bi3+。
6.根据权利要求1的催化剂,其中所述至少一种三价金属离子选自Fe3+、In3+、Sc3+、La3+、Ce3+、Pr3+、Nd3+、Sm3+、Eu3+、Gd3+、Tb3+、Dy3+、Ho3+、Er3+、Tm3+、Yb3+和Lu3+。
7.根据权利要求1的催化剂,其中所述至少一种三价金属离子包括至少两种三价金属离子的组合。
8.根据权利要求7的催化剂,其中所述至少两种三价金属离子包括三价过渡金属离子。
9.根据权利要求7的催化剂,其中至少一种三价金属离子包括三价过渡金属离子且其中至少一种其它三价金属离子包括三价镧系金属离子。
10.根据权利要求7的催化剂,其中至少一种三价金属离子包括三价过渡金属离子且其中至少一种其它三价金属离子包括三价主族金属离子。
11.根据权利要求7的催化剂,其中至少一种三价金属离子包括三价主族金属离子且其中至少一种其它三价金属离子包括三价镧系金属离子。
12.根据权利要求1的催化剂,其中所述沸石包括CuFe-SSZ-13。
13.根据权利要求1的催化剂,其中所述催化剂在150℃时呈现至少为60%的NOx转化率。
14.根据权利要求13的催化剂,其中所述催化剂还在200℃时呈现至少为85%的NOx转化率。
15.根据权利要求13的催化剂,其中所述催化剂还在600℃时呈现至少为65%的NOx转化率。
16.催化转化器,其包含负载于耐火材料基体上的催化剂,所述催化剂包含异双金属沸石,所述异双金属沸石的特征在于负载有铜离子和至少一种除Al3+之外的三价金属离子的菱沸石结构,且其中所述催化剂减少柴油废气中的NOx排放。
17.根据权利要求16的催化转化器,其中所述至少一种三价金属离子包括三价过渡金属离子。
18.根据权利要求17的催化转化器,其中所述三价过渡金属离子选自Sc3+、Y3+、V3+、Nb3+、Cr3+、Fe3+和Co3+。
19.根据权利要求16的催化转化器,其中所述至少一种三价金属离子包括三价主族金属离子。
20.根据权利要求19的催化转化器,其中所述三价主族金属离子选自Ga3+、In3+、As3+、Sb3+和Bi3+。
21.根据权利要求16的催化转化器,其中所述至少一种三价金属离子选自Fe3+、In3+、Sc3+、La3+、Ce3+、Pr3+、Nd3+、Sm3+、Eu3+、Gd3+、Tb3+、Dy3+、Ho3+、Er3+、Tm3+、Yb3+和Lu3+。
22.根据权利要求16的催化转化器,其中所述至少一种三价金属离子包括至少两种三价金属离子的组合。
23.根据权利要求22的催化转化器,其中所述至少两种三价金属离子包括三价过渡金属离子。
24.根据权利要求22的催化转化器,其中至少一种三价金属离子包括三价过渡金属离子且其中至少一种其它三价金属离子包括三价镧系金属离子。
25.根据权利要求22的催化转化器,其中至少一种三价金属离子包括三价过渡金属离子且其中至少一种其它三价金属离子包括三价主族金属离子。
26.根据权利要求22的催化转化器,其中至少一种三价金属离子包括三价主族金属离子且其中至少一种其它三价金属离子包括三价镧系金属离子。
27.根据权利要求16的催化转化器,其中所述沸石包括CuFe-SSZ-13。
28.根据权利要求16的催化转化器,其中所述催化剂在150℃时呈现至少为60%的NOx转化率。
29.根据权利要求28的催化转化器,其中所述催化剂在200℃时呈现至少为85%的NOx转化率。
30.根据权利要求28的催化转化器,其中所述催化剂在600℃时呈现至少为65%的NOx转化率。
31.根据权利要求16的催化转化器,其中所述耐火材料基体的特征在于选自棒状结构、蜂巢状结构和针轮状结构的结构。
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ES2960614T3 (es) | 2024-03-05 |
EP2827984A4 (en) | 2015-07-15 |
BR112014020419B1 (pt) | 2020-05-05 |
CA2865321A1 (en) | 2013-08-29 |
US9694352B2 (en) | 2017-07-04 |
EP2827984A1 (en) | 2015-01-28 |
US20150238946A1 (en) | 2015-08-27 |
HK1205046A1 (zh) | 2015-12-11 |
CN104220165B (zh) | 2016-08-24 |
CA2865321C (en) | 2020-01-28 |
WO2013126619A1 (en) | 2013-08-29 |
EP2827984B1 (en) | 2023-10-25 |
IN2014MN01632A (zh) | 2015-05-15 |
US9475039B2 (en) | 2016-10-25 |
US20170014814A1 (en) | 2017-01-19 |
US8987162B2 (en) | 2015-03-24 |
US20130224082A1 (en) | 2013-08-29 |
PL2827984T3 (pl) | 2024-04-08 |
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