WO2017134581A1 - Copper and iron co-exchanged chabazite catalyst - Google Patents
Copper and iron co-exchanged chabazite catalyst Download PDFInfo
- Publication number
- WO2017134581A1 WO2017134581A1 PCT/IB2017/050545 IB2017050545W WO2017134581A1 WO 2017134581 A1 WO2017134581 A1 WO 2017134581A1 IB 2017050545 W IB2017050545 W IB 2017050545W WO 2017134581 A1 WO2017134581 A1 WO 2017134581A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- zeolite
- catalyst
- iron
- copper
- cha
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 190
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052676 chabazite Inorganic materials 0.000 title claims abstract description 81
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound 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 title claims abstract description 77
- 239000010949 copper Substances 0.000 title claims abstract description 58
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 53
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 40
- 239000010457 zeolite Substances 0.000 claims abstract description 143
- 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 133
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 117
- 239000000203 mixture Substances 0.000 claims abstract description 86
- 238000000034 method Methods 0.000 claims abstract description 50
- 230000003197 catalytic effect Effects 0.000 claims abstract description 33
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- 230000009467 reduction Effects 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims description 80
- 229910052751 metal Inorganic materials 0.000 claims description 75
- 239000002184 metal Substances 0.000 claims description 75
- 239000002243 precursor Substances 0.000 claims description 60
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 229910021529 ammonia Inorganic materials 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 19
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 15
- 238000011068 loading method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical group [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 10
- 230000002829 reductive effect Effects 0.000 claims description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 241000269350 Anura Species 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011343 solid material Substances 0.000 claims description 4
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 112
- 239000007789 gas Substances 0.000 abstract description 73
- 239000000463 material Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000002002 slurry Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 239000010410 layer Substances 0.000 description 15
- 229910021645 metal ion Inorganic materials 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 14
- 239000004071 soot Substances 0.000 description 13
- 238000005342 ion exchange Methods 0.000 description 11
- 238000010531 catalytic reduction reaction Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000011144 upstream manufacturing Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 239000013618 particulate matter Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- -1 among others Chemical compound 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 239000002178 crystalline material Substances 0.000 description 3
- 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 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 229910052845 zircon Inorganic materials 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 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 2
- 238000001914 filtration Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000012692 Fe precursor Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 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 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 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
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 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
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000012243 magnesium silicates Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 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 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005303 weighing 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Definitions
- the present invention relates generally to the field of selective catalytic reduction catalysts and to methods of preparing and using such catalysts to selectively reduce nitrogen oxides.
- NO x is contained in exhaust gases, such as from internal combustion engines (e.g. , in automobiles and trucks), from combustion installations (e.g. , power stations heated by natural gas, oil, or coal), and from nitric acid production plants.
- internal combustion engines e.g. , in automobiles and trucks
- combustion installations e.g. , power stations heated by natural gas, oil, or coal
- Various treatment methods have been used for the treatment of NO x -containing gas mixtures to decrease atmospheric pollution.
- One type of treatment involves catalytic reduction of nitrogen oxides.
- a nonselective reduction process wherein carbon monoxide, hydrogen, or a lower hydrocarbon is used as a reducing agent
- a selective reduction process wherein ammonia or an ammonia precursor is used as a reducing agent.
- a high degree of nitrogen oxide removal can be achieved with a small amount of reducing agent.
- the selective reduction process is referred to as a SCR (Selective Catalytic Reduction) process.
- the SCR process uses catalytic reduction of nitrogen oxides with a reductant (e.g., ammonia) in the presence of atmospheric oxygen, resulting in the formation predominantly of nitrogen and steam:
- a reductant e.g., ammonia
- Catalysts employed in the SCR process ideally should be able to retain good catalytic activity over a wide range of temperature conditions of use, for example, 200 °C to 600 °C or higher, under hydrothermal conditions.
- SCR catalysts are commonly employed in hydrothermal conditions, such as during the regeneration of a soot filter, a component of the exhaust gas treatment system used for the removal of particles.
- zeolites have been used in the selective catalytic reduction of nitrogen oxides with a reductant such as ammonia, urea, or a hydrocarbon in the presence of oxygen.
- a reductant such as ammonia, urea, or a hydrocarbon in the presence of oxygen.
- Zeolites are crystalline materials having rather uniform pore sizes which, depending upon the type of zeolite and the type and amount of cations included in the zeolite lattice, range from about 3 to about 10 Angstroms in diameter.
- Certain zeolites having 8-ring pore openings and double-six ring secondary building units, particularly those having cage -like structures, have been used as SCR catalysts.
- zeolite having these properties is chabazite (CHA), which is a small pore zeolite with 8 member-ring pore openings (-3.8 Angstroms) accessible through its 3-dimensional porosity.
- CHA chabazite
- a cage-like structure results from the connection of double six-ring building units by 4 rings.
- Metal -promoted zeolite catalysts also often referred to ion-exchanged zeolites or zeolites supported with ireon and/or copper including, among others, iron-promoted and copper-promoted zeolite catalysts, for the selective catalytic reduction of nitrogen oxides with ammonia are known and can typically be prepared via metal ion-exchange processes.
- iron-promoted zeolite beta has been an effective commercial catalyst for the selective reduction of nitrogen oxides with ammonia.
- Metal-promoted, particularly copper-promoted, aluminosilicate zeolites having the CHA structure type have solicited a high degree of interest as catalysts for the SCR of oxides of nitrogen in lean burning engines using nitrogenous reductants. These materials exhibit activity within a wide temperature window and excellent hydrothermal durability, as described in U.S. Pat. No. 7,601,662.
- the present disclosure generally provides catalysts, catalytic articles and catalyst systems comprising such catalytic articles.
- such articles and systems comprise an SCR catalyst, which includes a combination of copper and iron co-exchanged on chabazite (CHA) zeolite material.
- SCR catalyst which includes a combination of copper and iron co-exchanged on chabazite (CHA) zeolite material.
- the catalyst includes a zeolite having a chabazite (CHA) crystal structure ion-exchanged with iron and copper.
- zeolite supports are often referred to as metal promoted supports, in this case iron promoted supports and/or copper promoted supports.
- the metal ions are supported metal ions, e.g. supported iron and copper. Therefore, the terms"ion-exchanged” and “supported iron and/or copper” can be used interchangeably.
- the pore size of the zeolite is about 3 to about 5 Angstroms. In another embodiment, the BET surface area of the zeolite is at least about 400 m 2 /g.
- the CHA crystal structure of the catalyst is selected from an
- the CHA crystal structure can be further selected from a group consisting of SSZ-13, SSZ-62, natural chabazite, zeolite K-G, Linde D, Linde R, LZ-218, LZ-235, LZ-236, ZK-14, SAPO-34, SAPO-4, SAPO-47, and ZYT-6.
- the CHA crystal structure of the catalyst is an aluminosilicate zeolite.
- the silica-to alumina ratio (SAR) of the aluminosilicate zeolite is about 5 to about 100, preferably about 10 to about 40, more preferably about 12 to about 35.
- the catalyst has a D90 particle size of about 10 to about 40 microns.
- the iron is present in the zeolite in an amount of from about 0.01% to about 6.0% by weight of the final metal ion-exchanged zeolite composition, preferably about 0.5% to about 4.5% by weight of the final metal ion-exchanged zeolite composition, more preferably about 1% to about 3.5% by weight of the final metal ion-exchanged zeolite composition, calculated as iron oxide (Fe 2 0 3 ).
- the copper is present in the zeolite in an amount of from about 0.01% to about 6.0% by weight of the final metal ion-exchanged zeolite composition, preferably about 0.5% to about 5% by weight of the final metal ion-exchanged zeolite composition, more preferably from about 1 % to about 4% by weight of the final metal ion-exchanged zeolite composition, calculated as copper oxide (CuO).
- the invention provides a method of making a CHA zeolite catalyst containing ion-exchanged iron and copper therein including the following steps: a) contacting a chabazite (CHA) zeolite with a copper metal precursor and an iron metal precursor in a solution to form a solid CHA zeolite material containing iron precursor and copper ion-exchanged therein; b) drying of the solid material to obtain a dry CHA zeolite catalyst containing iron and copper metal precursor therein; and
- the copper metal precursor described in this method is copper acetate.
- the iron metal precursor described in this method is iron (III) nitrate.
- the chabazite (CHA) zeolite in this method is a Na form of chabazite zeolite and has been calcined prior to contacting the copper metal precursor and the iron metal precursor.
- the copper metal precursor and iron metal precursor in solution is heated with the CHA zeolite at elevated temperature.
- the solution is an aqueous solution.
- the drying of the solid material occurs at elevated temperature.
- the CHA zeolite catalyst containing iron and copper metal precursors is calcined at a temperature of about 500 °C to about 800 °C.
- a catalyst article including a catalyst substrate having a plurality of channels adapted for gas flow, each channel having a wall surface in adherence to a catalytic coating comprising the catalyst composition.
- the catalyst substrate is a honeycomb.
- the honeycomb substrate includes a wall flow filter substrate.
- the honeycomb substrate includes a flow through substrate.
- the catalytic coating is present on the substrate with a loading of at least about 1.0 g/in 3 . In additional embodiments, the catalytic coating is present on the substrate with a loading of at least about 2.0 g in 3 .
- Another aspect of the invention describes a method for reducing NOx level in an exhaust gas including contacting the gas with the catalyst for a time and temperature sufficient to reduce the level of NOx in the gas.
- the NOx level in the exhaust gas is reduced to N 2 at a temperature between 200 °C to about 600 °C.
- the NOx level in the exhaust gas is reduced by at least 50% at 200 °C.
- the NOx level in the exhaust gas is reduced by at least 70% at 600 °C.
- the catalyst article is a selective reduction catalyst (SCR).
- an exhaust gas treatment system comprising the catalyst article disposed downstream from a combustion engine and an injector that adds a reductant to an exhaust gas from the engine.
- the engine is a diesel engine.
- the exhaust gas treatment system further includes a diesel oxidation catalyst.
- the reductant in the exhaust gas treatment system to include ammonia or an ammonia precursor.
- the invention includes, without limitation, the following embodiments.
- Embodiment 1 A catalyst composition comprising: a zeolite having a chabazite (CHA) crystal structure ion-exchanged with iron and copper.
- Embodiment 2 The catalyst composition of any preceding or subsequent embodiment, wherein said zeolite has a pore size of about 3 to about 5 Angstroms.
- Embodiment 3 The catalyst composition of any preceding or subsequent embodiment, wherein the CHA crystal structure is selected from an aluminosilicate zeolite, a borosilicate, a gallosilicate, a SAPO, and ALPO, a MeAPSO, and a MeAPO.
- Embodiment 4 The catalyst composition of any preceding or subsequent embodiment, wherein the CHA crystal structure is an aluminosilicate zeolite having a silica-to alumina ratio (SAR) of about 5 to about 100.
- SAR silica-to alumina ratio
- Embodiment 5 The catalyst composition of any preceding or subsequent embodiment, wherein said aluminosilicate zeolite has a silica-to alumina ratio (SAR) of about 10 to about 40.
- SAR silica-to alumina ratio
- Embodiment 6 The catalyst composition of any preceding or subsequent embodiment, wherein iron present in said zeolite in an amount of from about 0.01% to about 6.0% by weight of final metal ion- exchanged zeolite, calculated as iron oxide (Fe 2 03).
- Embodiment 7 The catalyst composition of any preceding or subsequent embodiment, wherein iron present in said zeolite in an amount of from about 0.5% to about 4.5% by weight of final metal ion- exchanged zeolite, calculated as iron oxide (Fe 2 03).
- Embodiment 8 The catalyst composition of any preceding or subsequent embodiment, wherein copper present in said zeolite in an amount of from about 0.01% to about 6.0% by weight of final metal ion- exchanged zeolite, calculated as copper oxide (CuO).
- Embodiment 9 The catalyst composition of any preceding or subsequent embodiment, wherein copper present in said zeolite in an amount of from about 0.5% to about 5% by weight of final metal ion- exchanged zeolite, calculated as copper oxide (CuO).
- Embodiment 10 The catalyst composition of any preceding or subsequent embodiment, wherein zeolite has a BET surface area of at least about 400 m 2 /g.
- Embodiment 11 The catalyst composition of any preceding or subsequent embodiment, having a D 90 particle size of about 10 to about 40 microns.
- Embodiment 12 A method of making a CHA zeolite catalyst containing iron and copper therein comprising: a. contacting a chabazite (CHA) zeolite with a copper metal precursor and an iron metal precursor in a solution to form a CHA zeolite material containing iron and copper therein; b. drying of said solid material to obtain a CHA zeolite catalyst containing iron and copper metal precursor therein; and c. calcining the CHA zeolite catalyst containing catalyst containing iron and copper metal precursor to convert the catalyst into active form.
- CHA chabazite
- Embodiment 13 The method of any preceding or subsequent embodiment, wherein the copper metal precursor is a copper acetate or copper nitrate salt.
- Embodiment 14 The method of any preceding or subsequent embodiment, wherein the iron metal precursor is an iron (III) nitrate or iron (II) acetate salt.
- Embodiment 15 The method of any preceding or subsequent embodiment, wherein the chabazite (CHA) zeolite is a Na form of chabazite zeolite and has been calcined prior to contacting the copper metal precursor and the iron metal precursor.
- chabazite (CHA) zeolite is a Na form of chabazite zeolite and has been calcined prior to contacting the copper metal precursor and the iron metal precursor.
- Embodiment 16 The method of any preceding or subsequent embodiment, further comprising heating the copper metal precursor and iron metal precursor in solution with the CHA zeolite at elevated temperature.
- Embodiment 17 The method of any preceding or subsequent embodiment, wherein the CHA zeolite catalyst containing catalyst containing iron and copper metal precursor is calcined at a temperature of about 500 °C to about 800 °C.
- Embodiment 18 The method of any preceding or subsequent embodiment, wherein solution is an aqueous solution.
- Embodiment 19 A catalyst article comprising a catalyst substrate having a plurality of channels adapted for gas flow, each channel having a wall surface in adherence to a catalytic coating comprising the catalyst composition of any preceding or subsequent embodiment.
- Embodiment 20 The catalyst article of any preceding or subsequent embodiment, wherein the catalyst substrate is a honeycomb substrate in the form of a wall flow filter substrate or a flow through substrate.
- Embodiment 21 The catalyst article of any preceding or subsequent embodiment, wherein catalytic coating is present on the substrate with a loading of at least about 1.0 g/in 3 .
- Embodiment 22 A method for reducing NOx level in an exhaust gas comprising contacting the gas with a catalyst for a time and temperature sufficient to reduce the level of NOx in the gas, wherein the catalyst is a catalyst composition according to any preceding or subsequent embodiment.
- Embodiment 23 The method of any preceding or subsequent embodiment, wherein said NOx level in the exhaust gas is reduced to N 2 at a temperature between 200 °C to about 600 °C.
- Embodiment 24 The method of any preceding or subsequent embodiment, wherein said NOx level in the exhaust gas is reduced by at least 50% at 200 °C.
- Embodiment 25 The method of any preceding or subsequent embodiment, wherein said NOx level in the exhaust gas is reduced by at least 70% at 600 °C.
- Embodiment 26 An emission treatment system for treatment of an exhaust gas stream, the emission treatment system comprising: (i) an engine producing an exhaust gas stream; (ii) a catalyst article according of any preceding or subsequent embodiment positioned downstream from the engine in fluid communication with the exhaust gas stream and adapted for the reduction of NOx within the exhaust stream to form a treated exhaust gas stream; and (iii) an injector adapted for the addition of a reductant to the exhaust gas stream to promote reduction of NOx to N 2 and water as the exhaust gas stream is exposed to the catalyst article.
- Embodiment 27 The emission treatment system of any preceding or subsequent embodiment, wherein the engine is a diesel engine.
- Embodiment 28 The emission treatment system of any preceding or subsequent embodiment, further comprising a diesel oxidation catalyst.
- Embodiment 29 The emission treatment system of any preceding or subsequent embodiment, wherein the reductant comprises ammonia or an ammonia precursor.
- FIG. 1 is a perspective view of a honeycomb-type substrate carrier which may comprise a catalytic article (i.e., selective reduction catalyst (SCR)) washcoat composition in accordance with the present invention
- a catalytic article i.e., selective reduction catalyst (SCR)
- SCR selective reduction catalyst
- FIG. 2 is a partial cross-sectional view enlarged relative to FIG. 1 and taken along a plane parallel to the end faces of the substrate carrier of FIG. 1 representing a monolithic flow-through substrate, which shows an enlarged view of a plurality of the gas flow passages shown in FIG. 1 ;
- FIG. 3 is a cutaway view of a section enlarged relative to FIG. 1 , wherein the honeycomb-type substrate carrier in FIG.l represents a wall flow filter substrate monolith;
- FIG. 4 shows a schematic depiction of an embodiment of an emission treatment system in which an SCR of the present invention is utilized.
- DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention now will be described more fully hereinafter. This invention may, however, be embodied in many different forms and should not be construed as limited to the
- the present invention provides a selective reduction catalyst (SRC) composition suitable for at least partial conversion of gaseous NOx emissions and a reduction in N 2 0 make.
- the SRC composition includes at least two metal oxide components ion-exchanged on a porous refractory oxide support that provide an effect on NOx conversion activity.
- the SRC composition can be prepared using metal ion- exchange processes rather than incipient wetness impregnation techniques to generate the catalyst composition, which can then be coated onto a catalyst substrate using a washcoat technique as set forth more fully below.
- Ion exchange is a process commonly used for exchanging ions residing in a porous support with an outside metal ion of interest.
- zeolites prepared with sodium ions residing in the pores can be exchanged with a different ion to form an ion-exchanged porous support. This is accomplished by preparing a slurry of the porous support, i.e., zeolite, in a solution containing the outside metal ion of interest to be exchanged. Heat may be optionally applied during this process.
- the outside metal ion can diffuse into the pores of the support and exchange with the residing ion, i.e., sodium, to form the metal- ion exchanged porous support.
- incipient wetness impregnation techniques also called capillary impregnation or dry impregnation, commonly used for the synthesis of heterogeneous materials, i.e., catalysts
- capillary impregnation or dry impregnation commonly used for the synthesis of heterogeneous materials, i.e., catalysts
- a metal precursor is dissolved in an aqueous or organic solution and then the metal-containing solution is added to a catalyst support, i.e., zeolite, containing the same pore volume as the volume of the solution that was added.
- Capillary action draws the solution into the pores of the support.
- Solution added in excess of the support pore volume causes the solution transport to change from a capillary action process to a diffusion process, which is much slower.
- the catalyst can then be dried and calcined to drive off the volatile components within the solution, depositing the metal on the catalyst surface.
- the maximum loading is limited by the solubility of the precursor in the solution.
- the concentration profile of the impregnated material depends on the mass transfer conditions within the pores during impregnation and drying.
- SCR selective catalytic reduction
- the term "catalyst” or “catalyst composition” refers to a material that promotes a reaction.
- the phrase “catalyst system” refers to a combination of two or more catalysts, for example a combination of a first SCR catalyst and a second SCR catalyst.
- the catalyst system may be in the form of a washcoat in which the two SCR catalysts are mixed together.
- upstream and downstream refer to relative directions according to the flow of an engine exhaust gas stream from an engine towards a tailpipe, with the engine in an upstream location and the tailpipe and any pollution abatement articles such as filters and catalysts being downstream from the engine.
- gas stream broadly refers to any combination of flowing gas that may contain solid or liquid particulate matter.
- gaseous stream or “exhaust gas stream” means a stream of gaseous constituents, such as the exhaust of a lean burn engine, which may contain entrained non-gaseous components such as liquid droplets, solid particulates, and the like.
- the exhaust gas stream of a lean burn engine typically further comprises combustion products, products of incomplete combustion, oxides of nitrogen, combustible and/or carbonaceous particulate matter (soot), and un- reacted oxygen and nitrogen.
- the term "substrate” refers to the monolithic material onto which the catalyst composition is placed, typically in the form of a washcoat containing a plurality of particles containing a catalytic composition thereon.
- a washcoat is formed by preparing slurry containing a certain solid content (e.g., 30-90% by weight) of particles in a liquid vehicle, which is then coated onto a substrate and dried to provide a washcoat layer.
- washcoat has its usual meaning in the art of a thin, adherent coating of a catalytic or other material applied to a substrate material, such as a honeycomb-type carrier member, which is sufficiently porous to permit the passage of the gas stream being treated.
- catalytic article refers to an element that is used to promote a desired reaction.
- a catalytic article may comprise a washcoat containing catalytic compositions on a substrate.
- amalgamate means to decrease in amount and "abatement” means a decrease in the amount, caused by any means.
- impregnated or “impregnation” refers to permeation of the catalytic material into the porous structure of the support material.
- porous structure As used therein, the term “pseudo crystalline” refers to a substance that appears to be crystalline, even under a microscope, but does not have a true crystalline diffraction pattern.
- the SRC composition includes a combination of copper and iron ion-exchanged on a chabazite
- the combination of copper and iron ion-exchanged on a chabazite (CHA) zeolite support is expressed as a weight ratio of the corresponding metal oxides.
- that expressed weight ratio of copper oxide to iron oxide ranges from about 1:10 to about 10:1, more typically from about 1:3 to about 3: 1.
- the concentrations of copper and iron components can vary, but will typically be from about 0.1 wt.% to about 12 wt.% relative to the weight of the zeolite support material (e.g., about 6 wt.% to about 8 wt. % relative to the final metal ion-exchanged zeolite support composition) calculated as the metal oxide.
- the iron present in the zeolite is in an amount of from about 0.01% to about 6.0% by weight of the final metal-ion exchanged zeolite composition, preferably about 0.5% to about 4.5% by weight of the final metal-ion exchanged zeolite composition, more preferably about 1% to about 3.5% by weight of the final metal-ion exchanged zeolite composition, calculated as iron oxide (Fe 2 03).
- the copper present in said zeolite is in an amount of from about 0.01% to about 6.0% by weight of the final metal-ion exchanged zeolite composition, preferably about 0.5% to about 5.0% by weight of the final metal-ion exchanged zeolite composition, more preferably about 1% to about 4% by weight of the final metal -ion exchanged zeolite composition, calculated as copper oxide (CuO).
- CuO copper oxide
- These newly formed zeolite supports are often referred to as metal promoted supports, in this case iron promoted supports and/or copper promoted supports.
- these metal ions are supported metal ions, e.g. supported iron and copper.
- Zeolites of the present invention are chabazite (CHA) crystal structure zeolites and selected from an aluminosilicate zeolite, a borosilicate, a gallosilicate, a SAPO, and ALPO, a MeAPSO, and a MeAPO.
- the CHA crystal structure is an aluminosilicate zeolite.
- Aluminosilicate zeolites can have a crystalline or pseudo crystalline structure and may include framework metals other than aluminum (i.e., metal-substituted), such as silico-aluminophosphates (SAPOs).
- SAPOs silico-aluminophosphates
- Natural as well as synthetic zeolites may also be used, but synthetic zeolites are preferred because these zeolites have more uniform silica-alumina ratio (SAR), crystallite size, and crystallite morphology, and have fewer and less concentrated impurities (e.g. alkaline earth metals).
- Specific zeolites having the CHA structure that are useful in the present invention include, but are not limited to SSZ-13, SSZ-62, natural chabazite, zeolite K-G, Linde D, Linde R, LZ-218, LZ-235, LZ-236, ZK-14, SAPO-34, SAPO-4, SAPO-47, and ZYT-6.
- Zeolites being crystalline materials have rather uniform pore sizes which, depending upon the type of zeolite and the type and amount of cations included in the zeolite lattice, range from about 3 to 10 Angstroms in diameter.
- the CHA zeolite has a pore size of about 3 to about 5 Angstroms.
- the zeolite is typically present in the form of a highly crystalline material, the material being at least about 75% crystalline, at least about 80% crystalline, at least about 85% crystalline, at least about 90% crystalline, at least about 95% crystalline, at least about 98% crystalline, at least about 99% crystalline, or at least about 99.5% crystalline.
- the synthesis of zeolite varies according to the structure type of the molecular sieve material, but is usually synthesized using a structure directing agent (SDA), sometimes referred to as a template (or organic template) together with sources of silica and alumina.
- SDA structure directing agent
- the structure directing agent can be in the form of an organic, i.e.
- tetraethylammonium hydroxide TEAOH
- inorganic cation i.e. Na + or K + .
- the tetrahedral units organize around the SDA to form the desired framework, and the SDA is often embedded within the pore structure of the zeolite crystals.
- the crystallization of the first and second molecular sieves can be obtained by means of the addition of structure-directing agents/templates, crystal nuclei or elements. Exemplary preparations of zeolites are described in U.S. Pat. No. 8,293,198 to Beutel et al.; U.S. Pat. No. 8,715,618 of Trukhan et al.; U.S. Pat. No. 9,162,218 of Bull et al.; and U.S. Pat. No.
- Zeolites generally comprise silica to alumina (SAR) molar ratios of 2 or greater.
- SAR silica to alumina
- the ratio of silica to alumina of the molecular sieve components can vary over a wide range.
- molecular sieves e.g. zeolites
- zeolites are defined as aluminosilicates with open 3- dimensional framework structures composed of corner-sharing TO 4 tetrahedra, where T is Al or Si.
- Cations that balance the charge of the anionic framework are loosely associated with the framework oxygens, and the remaining pore volume is filled with water molecules.
- the non-framework cations are generally exchangeable, and the water molecules removable.
- Zeolite support material typically exhibits a BET surface area in excess of 60 m 2 /g, often up to about 200 m 2 /g or higher.
- BET surface area has its usual meaning of referring to the Brunauer, Emmett, Teller method for determining surface area by N 2 adsorption. In one or more embodiments the BET surface area is at least about 200 m 2 /g, or at least about 400 m 2 /g, or at least about 600 m 2 /g.
- the particle size of the zeolite can vary. Generally the particle size of CHA zeolite can be characterized by a D90 particle size of about 10 to about 40 microns, preferably about 10 to about 30 microns, more preferably 10 microns to about 20 microns. D90 is defined as the particle size at which 90% of the particles have a finer particle size.
- a Cu/Fe co-exchanged chabazite catalyst can be prepared by a one-step direct co-exchange of a calcined Na form of chabazite zeolite.
- the Na form zeolite should be preferably calcined prior to the exchange at the lowest practical temperature ( ⁇ 540°C) to eliminate or minimize formation of the extra-framework aluminum species and/or distorted aluminum sites.
- the co-exchange can be performed at 60°C for 1 hr using copper acetate and iron (III) nitrate as metal precursors.
- the copper acetate can be added first, followed by the addition of the iron (III) nitrate nonahydrate. While the Fe(III) exchanges nominally at 100%, the proper amount of Cu-acetate can be pre-determined using an ion exchange isotherm. After the exchange is completed, the sample is filtered and washed using a
- the substrate for the catalyst article composition may be constructed of any material typically used for preparing automotive catalysts and will typically comprise a metal or ceramic honeycomb structure.
- the substrate typically provides a plurality of wall surfaces upon which the catalyst article (i.e., SRC catalyst) washcoat composition is applied and adhered, thereby acting as a carrier for the catalyst composition.
- Exemplary metallic substrates include heat resistant metals and metal alloys, such as titanium and stainless steel as well as other alloys in which iron is a substantial or major component.
- Such alloys may contain one or more of nickel, chromium, and/or aluminum, and the total amount of these metals may advantageously comprise at least 15 wt. % of the alloy, e.g., 10-25 wt. % of chromium, 3-8 wt. % of aluminum, and up to 20 wt. % of nickel.
- the alloys may also contain small or trace amounts of one or more other metals, such as manganese, copper, vanadium, titanium and the like.
- the surface or the metal carriers may be oxidized at high temperatures, e.g., 1000°C and higher, to form an oxide layer on the surface of the substrate, improving the corrosion resistance of the alloy and facilitating adhesion of the washcoat layer to the metal surface.
- Ceramic materials used to construct the substrate may include any suitable refractory material, e.g., cordierite, mullite, cordierite-a alumina, silicon nitride, zircon mullite, spodumene, alumina-silica magnesia, zircon silicate, sillimanite, magnesium silicates, zircon, petalite, a alumina, aluminosilicates and the like.
- Any suitable substrate may be employed, such as a monolithic flow-through substrate having a plurality of fine, parallel gas flow passages extending from an inlet to an outlet face of the substrate such that passages are open to fluid flow.
- the passages which are essentially straight paths from the inlet to the outlet, are defined by walls on which the catalytic material is coated as a washcoat so that the gases flowing through the passages contact the catalytic material.
- the flow passages of the monolithic substrate are thin-walled channels which can be of any suitable cross-sectional shape, such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, circular, and the like. Such structures may contain from about 60 to about 1200 or more gas inlet openings (i.e., "cells") per square inch of cross section (cpsi), more usually from about 300 to 600 cpsi.
- the wall thickness of flow-through substrates can vary, with a typical range being between 0.002 and 0.1 inches.
- a representative commercially-available flow-through substrate is a cordierite substrate having 400 cpsi and a wall thickness of 6 mil, or 600 cpsi and a wall thickness of 4 mil.
- the invention is not limited to a particular substrate type, material, or geometry.
- the substrate may be a wall-flow substrate, wherein each passage is blocked at one end of the substrate body with a non-porous plug, with alternate passages blocked at opposite end-faces. This requires that gas flow through the porous walls of the wall-flow substrate to reach the exit.
- Such monolithic substrates may contain up to about 700 or more cpsi, such as about 100 to 400 cpsi and more typically about 200 to about 300 cpsi.
- the cross-sectional shape of the cells can vary as described above.
- Wall -flow substrates typically have a wall thickness between 0.002 and 0.1 inches.
- a representative commercially available wall-flow substrate is constructed from a porous cordierite, an example of which has 200 cpsi and 10 mil wall thickness or 300 cpsi with 8 mil wall thickness, and wall porosity between 45-65%.
- Other ceramic materials such as aluminum-titanate, silicon carbide and silicon nitride are also used a wall-flow filter substrates.
- the invention is not limited to a particular substrate type, material, or geometry. Note that where the substrate is a wall-flow substrate, the catalyst article (i.e. SCR catalyst) composition can permeate into the pore structure of the porous walls (i.e., partially or fully occluding the pore openings) in addition to being disposed on the surface of the walls.
- FIGS. 1 and 2 illustrate an exemplary substrate 2 in the form of a flow-through substrate coated with a washcoat composition as described herein.
- the exemplary substrate 2 has a cylindrical shape and a cylindrical outer surface 4, an upstream end face 6 and a corresponding downstream end face 8, which is identical to end face 6.
- Substrate 2 has a plurality of fine, parallel gas flow passages 10 formed therein.
- flow passages 10 are formed by walls 12 and extend through carrier 2 from upstream end face 6 to downstream end face 8, the passages 10 being unobstructed so as to permit the flow of a fluid, e.g., a gas stream, longitudinally through carrier 2 via gas flow passages 10 thereof.
- a fluid e.g., a gas stream
- the washcoat composition can be applied in multiple, distinct layers if desired.
- the washcoat consists of both a discrete bottom washcoat layer 14 adhered to the walls 12 of the carrier member and a second discrete top washcoat layer 16 coated over the bottom washcoat layer 14.
- the present invention can be practiced with one or more (e.g., 2, 3, or 4) washcoat layers and is not limited to the illustrated two-layer embodiment.
- FIGS. 1 and 3 can illustrate an exemplary substrate 2 in the form a wall flow filter substrate coated with a washcoat composition as described herein.
- the exemplary substrate 2 has a plurality of passages 52.
- the passages are tubularly enclosed by the internal walls 53 of the filter substrate.
- the substrate has an inlet end 54 and an outlet end 56.
- Alternate passages are plugged at the inlet end with inlet plugs 58, and at the outlet end with outlet plugs 60 to form opposing checkerboard patterns at the inlet 54 and outlet 56.
- a gas stream 62 enters through the unplugged channel inlet 64, is stopped by outlet plug 60 and diffuses through channel walls 53 (which are porous) to the outlet side 66.
- the porous wall flow filter used in this invention is catalyzed in that the wall of said element has thereon or contained therein one or more catalytic materials.
- Catalytic materials may be present on the inlet side of the element wall alone, the outlet side alone, both the inlet and outlet sides, or the wall itself may consist all, or in part, of the catalytic material.
- This invention includes the use of one or more layers of catalytic material on the inlet and/or outlet walls of the element.
- the total loading of the catalytic article (i.e., both ion-exchanged metals on zeolite support material) on the catalyst substrate, such as a monolithic flow-through substrate, is typically from about 0.5 to about 6 g/in 3 , and more typically from about 1 to about 5 g/in 3 . It is noted that these weights per unit volume are typically calculated by weighing the catalyst substrate before and after treatment with the catalyst washcoat composition, and since the treatment process involves drying and calcining the catalyst substrate at high temperature, these weights represent an essentially solvent-free catalyst coating as essentially all of the water of the washcoat slurry has been removed.
- Preparation of the metal ion-exchanged zeolite material typically comprises an ion-exchange process of the zeolite support material in particulate form with a metal precursor solution.
- Multiple metal precursors e.g., copper and iron
- CHA zeolite particles are used as support particles.
- the ion exchange isotherm describes the concentration of the first metal ion precursor as a function of its concentration in the external solution at any given temperature and pressure.
- Complete co-exchange of the first metal precursor ion with the ions residing in the support material is achieved when the ion concentration of the first metal precursor is at an effective concentration in the external solution to promote complete such ion exchange at a given temperature and pressure.
- the second metal precursor is added to the same external solution to allow for co- exchange of the ions of the second metal precursor.
- the support particles are usually sufficiently dry to absorb substantially all of the solution to form a moist solid.
- a Na form of chabazite zeolite can be calcined to afford dry Na-chabazite zeolite prior to contact with the precursor metals.
- Aqueous solutions of water soluble compounds or complexes of the metal precursors are typically utilized, such as nitrate or acetate salts of the metal precursors with specific examples including copper (II) nitrate, copper (II) acetate, iron (II) acetate, iron (III) nitrate, and iron (III) acetate.
- the particles are dried, such as by heat treating the particles at elevated temperature (e.g., 100-150°C) for a period of time (e.g., 1-3 hours), and then calcining to convert the metal components to a more catalytically active oxide form.
- elevated temperature e.g., 100-150°C
- a period of time e.g., 1-3 hours
- An exemplary calcination process involves heat treatment in air at a temperature of about 500-800°C for about 1-3 hours. The above process can be repeated as needed to reach the desired level of metal precursor impregnation.
- the resulting material can be stored as a dry powder or in slurry form.
- the above-noted catalyst composition in the form of carrier particles containing a combination of metal components ion-exchanged therein, is mixed with water to form a slurry for purposes of coating a catalyst substrate, such as a honeycomb-type substrate.
- the slurry may optionally contain alumina as a binder, water-soluble or water-dispersible stabilizers (e.g., barium acetate), promoters (e.g., lanthanum nitrate), associative thickeners, and/or surfactants (including anionic, cationic, non-ionic or amphoteric surfactants).
- the alumina binder is typically used in an amount of about 0.05 g/in 3 to about 1 g/in 3 .
- the alumina binder can be, for example, boehmite, gamma-alumina, or delta/theta alumina.
- the slurry can be milled to enhance mixing of the particles and formation of a homogenous material.
- the milling can be accomplished in a ball mill, continuous mill, or other similar equipment, and the solids content of the slurry may be, e.g., about 20-60 wt. %, more particularly about 30-40 wt. %.
- the post-milling slurry is characterized by a D90 particle size of about 10 to about 40 microns, preferably 10 to about 30 microns, more preferably about 10 to about 15 microns.
- the D90 is defined as the particle size at which 90% of the particles have a finer particle size.
- the slurry is then coated on the catalyst substrate using a washcoat technique known in the art.
- the catalyst substrate is dipped one or more times in the slurry or otherwise coated with the slurry. Thereafter, the coated substrate is dried at an elevated temperature (e.g., 100-150°C) for a period of time (e.g., 1-3 hours) and then calcined by heating, e.g., at 400-600° C, typically for about 10 minutes to about 3 hours. Following drying and calcining, the final washcoat coating layer can be viewed as essentially solvent-free.
- the catalyst loading obtained by the above described washcoat technique can be determined through calculation of the difference in coated and uncoated weights of the substrate.
- the catalyst loading can be modified by altering the slurry rheology.
- the coating/drying/calcining process to generate a washcoat can be repeated as needed to build the coating to the desired loading level or thickness, meaning more than one washcoat may be applied.
- the catalyst composition can be applied as a single layer or in multiple layers. In one embodiment, the catalyst is applied in a single layer (e.g., only layer 14 of FIG. 2). In another embodiment, the catalyst composition is applied in multiple layers (e.g., layers 14 and 16 of FIG. 2).
- the present invention also provides an emission treatment system that incorporates the SRC catalyst composition (i.e., catalytic article) described herein.
- the SRC catalyst composition of the present invention is typically used in an integrated emissions treatment system comprising one or more additional components for the treatment of exhaust gas emissions, e.g., exhaust gas emissions from a diesel engine.
- the emission treatment system may further comprise a catalyzed soot filter (CSF) component and/or a selective diesel oxidation (DOC) catalytic article.
- CSF catalyzed soot filter
- DOC selective diesel oxidation
- the SRC catalyst of the invention is typically located upstream or downstream from the soot filter and downstream from the diesel oxidation catalyst component, although the relative placement of the various components of the emission treatment system can be varied.
- the treatment system includes further components, such as reductant injectors for ammonia precursors, and may optionally include any additional particulate filtration components, NO x storage and/or trapping components.
- reductant injectors for ammonia precursors may optionally include any additional particulate filtration components, NO x storage and/or trapping components.
- the CSF may comprise a substrate coated with a washcoat layer containing one or more catalysts for burning trapped soot and or oxidizing exhaust gas stream emissions.
- the soot burning catalyst can be any known catalyst for combustion of soot.
- the CSF can be catalyzed with one or more high surface area refractory oxides (e.g., an alumina or a zirconia oxide) and/or an oxidation catalyst (e.g., a ceria-zirconia) for the combustion of unburned hydrocarbons and to some degree particulate matter.
- the soot burning catalyst can be an oxidation catalyst comprising one or more precious metal catalysts (e.g., platinum, palladium, and/or rhodium).
- the CSF may comprise a substrate coated with a washcoat layer containing one or more catalysts for reducing NOx in the exhaust gas stream emissions.
- the CSF can be catalyzed with one or more selective reduction catalysts for the conversion of NOx in the exhaust gas stream in addition to containing one or more layers containing one or more catalysts for burning trapped soot and or oxidizing exhaust gas stream emissions.
- FIG. 4 depicts a schematic representation of an emission treatment system 32.
- an exhaust gas stream containing gaseous pollutants and particulate matter is conveyed via exhaust pipe 36 from an engine 34 to a diesel oxidation catalyst (DOC) 38 to a catalyzed soot filter (CSF) to a selective reductive catalyst (SRC), which is coated with the washcoat composition of the present invention.
- DOC 38 diesel oxidation catalyst
- CSF catalyzed soot filter
- SRC selective reductive catalyst
- unburned gaseous and nonvolatile hydrocarbons (i.e., the SOF) and carbon monoxide are largely combusted to form carbon dioxide and water.
- a proportion of the NO of the NO x component may be oxidized to NO 2 in the DOC.
- the exhaust stream is next conveyed via exhaust pipe 40 to a catalyzed soot filter (CSF) 42, which traps particulate matter present within the exhaust gas stream.
- CSF 42 is optionally catalyzed for passive or active soot regeneration.
- the CSF 42 can optionally include a SRC composition for the conversion of NOx present in the exhaust gas.
- the exhaust gas stream is conveyed via exhaust pipe 44 to a downstream selective catalytic reduction (SCR) component 46 of the invention for the further treatment and/or conversion of NO x .
- SCR selective catalytic reduction
- the exhaust gas passes through the SCR component 46 at a flow rate which allows sufficient time for the catalyst composition to reduce the level of NOx in the exhaust gas at a given temperature.
- the SCR component 46 may optionally be included in the emission treatment system when CSF 42 already includes an SRC composition.
- An injector 50 for introducing a nitrogenous reducing agent into the exhaust stream is located upstream of the SRC 46. In some embodiments, the injector 50 may also be introduced upstream of the CSF 42 provided that the CSF 42 includes an SCR composition. The introduced nitrogenous reducing agent into the gas exhaust stream promotes the reduction of the NOx to N 2 and water as the gas is exposed to the catalyst composition.
- a method for the reduction of NO x in an exhaust gas which comprises contacting the exhaust gas with the catalyst composition described herein and optionally in the presence of a reductant for a time and temperature sufficient to catalytically reduce NO x thereby lowering the concentration of NO x in the exhaust gas.
- the temperature range is from about 200 °C to about 600 °C.
- the catalyst composition of the invention reduces the level of NOx in the exhaust gas by at least about 50%.
- the catalyst composition of the invention reduces the level of NOx in the exhaust gas by at least about 70%.
- the amount of NOx reduction is dependent upon the contact time of the exhaust gas stream with the catalyst, and thus is dependent upon the space velocity.
- the contact time and space velocity is not particularly limited in the present invention.
- the present catalyst composition of the invention has shown increased NOx reduction compared to commercial reference SCR catalysts. As such, the catalyst composition can perform, well even at high space velocity, which is desirable in certain applications.
- a nitrogenous reducing agent may be introduced into the exhaust gas prior to contacting the SRC catalyst for the treatment of NOx.
- this reducing agent for SCR processes broadly means any compound that promotes the reduction of NOx in an exhaust gas.
- reductants include ammonia, hydrazine or any suitable ammonia precursor such as urea ((NH 2 ) 2 CO), ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate or ammonium formate.
- the nitrogenous reducing agent is added using a reductant injector, which adds ammonia precursor to the gas exhaust stream upstream of the SRC 46. The presence of ammonia or the ammonia precursor in the gas exhaust stream promotes the reduction of the NOx to N 2 and water as the gas is exposed to the catalyst composition.
- the following examples are directed towards Cu/Fe co-exchanged chabazite (CHA) catalysts intended for use in diesel NOx abatement applications - the examples provide a method of preparation and illustrate improved high temperature SCR performance obtained on coated cores with nominal loading (dry gain) of 2.1 g/in 3 .
- CHA Cu/Fe co-exchanged chabazite
- Dry Na-chabazite zeolite was prepared by calcinating Na-chabazite zeolite at the lowest practical temperature ( ⁇ 540°C) to eliminate or minimize formation of the extra-framework aluminum species and/or distorted aluminum sites to afford dry calcined Na-chabazite zeolite.
- the calcined Na-chabazite zeolite was placed in a reaction vessel, followed by the addition of deionized water, and copper acetate, while mixing. Iron (III) nitrate nonahydrate was added last. The reaction mixture was heated to 60 °C for about 1 hour. Exchange of iron (III) nitrate with the sodium ions present in the zeolite occurred with 100% conversion. The amount of copper acetate was pre-determined using an ion exchange isotherm. After the ion exchange was complete, the sample was filtered and washed using a Buchner funnel to ⁇ 200 ⁇ conductivity, and then dried at 85°C in the drying oven. Copper and iron contents of the zeolite material were analyzed using ICP and are reported as oxides on a volatile free basis (see Table 1).
- Co-exchanged samples of the zeolite material were coated next on cores.
- a slurry was prepared by mixing Cu/Fe co-exchanged Chabazite (1 part in grams) with deionized water (1.5 part in grams). Zirconium acetate was added to the slurry as a solution in the amount of 5% by wt. of the Cu/Fe co- exchanged Chabazite amount already present in the slurry.
- the slurry was shear mixed at 2500 rpm for 30 minutes. Octanol (1-2 drops) may be added to defoam the stirring slurry.
- the slurry was coated onto 13x13x3 in 3 cellular ceramic cores, having a cell density of 400 cpsi (cells per square inch) and a wall thickness of 6 mil.
- the cores were dip coated and dried at 130 °C for 4 minutes and coated again if needed to obtain a washcoat loading of 2.1 g/in 3 and calcined at 450 °C for 1 hour.
- EXAMPLE 2 Evaluation of a Cu/Fe co-exchanged Chabazite (CHA) catalyst as an SCR catalyst for decreasing diesel NOx.
- CHA Cu/Fe co-exchanged Chabazite
- Nitrogen oxides selective catalytic reduction (SCR) efficiency of a fresh catalyst core was measured by adding a feed gas mixture of 500 ppm of NO, 500 ppm of NH 3 , 10% O2 (by volume), 5% H 2 0( by volume), balance N 2 to a steady state reactor containing a core of Example 1.
- the washcoated cores (dimensions: 3 inches long X 3 ⁇ 4 inches wide X 3 ⁇ 4 inches high) were wrapped with a ceramic insulation mat and placed inside an Inconel reactor tube heated by an electrical furnace.
- the gases, O2 (from air), N 2 and H 2 0 were preheated in a preheater furnace before entering the reactor.
- the reactive gases NO and NH 3 were introduced between the preheater furnace and the reactor.
- the reaction was carried at a space velocity of 80,000 If 1 across a 200° C to 600° C temperature range. Space velocity is defined as the gas flow rate comprising the entire reaction mixture divided by the geometric volume of the catalyst core. These conditions define the standard test for fresh catalysts.
- Results are summarized in Table 1.
- minimal changes of NOx conversion at 200 °C were detected as the amount of iron oxide loading increased in the SCR composition (e.g., Catalyst 2 versus Catalyst 4).
- NOx conversion improved upon increase of iron oxide loading by about 10% compared to the commercial reference material (e.g., commercial reference versus Catalyst 4).
- an increase of total metal loading of the SRC composition also exhibited and increase in the amount of NOx conversion at 600 °C.
Abstract
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RU2018131407A RU2018131407A (en) | 2016-02-03 | 2017-02-01 | CHABASITIC CATALYST JOINTLY EXCHANGED FOR COPPER AND IRON |
JP2018540754A JP6925350B2 (en) | 2016-02-03 | 2017-02-01 | Copper and iron co-exchanged chabazite catalyst |
CN201780019587.2A CN108883403A (en) | 2016-02-03 | 2017-02-01 | The chabasie catalyst that copper and iron exchange altogether |
BR112018015842-9A BR112018015842B1 (en) | 2016-02-03 | 2017-02-01 | CATALYST COMPOSITION, METHODS FOR PRODUCING A CATALYST AND FOR REDUCING THE NOX LEVEL IN AN EXHAUST GAS, CATALYST ARTICLE AND EMISSION TREATMENT SYSTEM |
KR1020187025273A KR20180102199A (en) | 2016-02-03 | 2017-02-01 | Copper and iron co-exchanged chabazite catalysts |
MX2018009534A MX2018009534A (en) | 2016-02-03 | 2017-02-01 | Copper and iron co-exchanged chabazite catalyst. |
CA3013546A CA3013546A1 (en) | 2016-02-03 | 2017-02-01 | Copper and iron co-exchanged chabazite catalyst |
EP17747081.2A EP3411145A4 (en) | 2016-02-03 | 2017-02-01 | Copper and iron co-exchanged chabazite catalyst |
US16/053,111 US11311867B2 (en) | 2016-02-03 | 2018-08-02 | Copper and iron co-exchanged chabazite catalyst |
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