GB2507006A - Small pore molecular sieve supported copper catalysts - Google Patents
Small pore molecular sieve supported copper catalysts Download PDFInfo
- Publication number
- GB2507006A GB2507006A GB1320065.4A GB201320065A GB2507006A GB 2507006 A GB2507006 A GB 2507006A GB 201320065 A GB201320065 A GB 201320065A GB 2507006 A GB2507006 A GB 2507006A
- Authority
- GB
- United Kingdom
- Prior art keywords
- catalyst
- molecular sieve
- scr
- lean
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 202
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 153
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 239000010949 copper Substances 0.000 title claims abstract description 90
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 46
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011148 porous material Substances 0.000 title description 84
- 238000000034 method Methods 0.000 claims abstract description 37
- 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 19
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 9
- 238000002485 combustion reaction Methods 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 5
- 239000010970 precious metal Substances 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 15
- 230000008929 regeneration Effects 0.000 claims description 13
- 238000011069 regeneration method Methods 0.000 claims description 13
- 239000004071 soot Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003502 gasoline Substances 0.000 claims description 3
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 3
- 239000003949 liquefied natural gas Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 229910052728 basic metal Inorganic materials 0.000 abstract 1
- 150000003818 basic metals Chemical class 0.000 abstract 1
- 230000032683 aging Effects 0.000 description 52
- 230000000694 effects Effects 0.000 description 49
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 32
- 230000000977 initiatory effect Effects 0.000 description 27
- 238000001311 chemical methods and process Methods 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- 239000000376 reactant Substances 0.000 description 20
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 15
- 230000009467 reduction Effects 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 14
- 239000003638 chemical reducing agent Substances 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 229910018557 Si O Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 229910052676 chabazite Inorganic materials 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 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 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 231100000812 repeated exposure Toxicity 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- -1 i.e. Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 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
- 229910052684 Cerium Inorganic materials 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012993 chemical processing Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 229910052675 erionite Inorganic materials 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000018537 nitric oxide storage Effects 0.000 description 2
- 229910001744 pollucite Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- WRRSFOZOETZUPG-FFHNEAJVSA-N (4r,4ar,7s,7ar,12bs)-9-methoxy-3-methyl-2,4,4a,7,7a,13-hexahydro-1h-4,12-methanobenzofuro[3,2-e]isoquinoline-7-ol;hydrate Chemical compound O.C([C@H]1[C@H](N(CC[C@@]112)C)C3)=C[C@H](O)[C@@H]1OC1=C2C3=CC=C1OC WRRSFOZOETZUPG-FFHNEAJVSA-N 0.000 description 1
- OVGWMUWIRHGGJP-WVDJAODQSA-N (z)-7-[(1s,3r,4r,5s)-3-[(e,3r)-3-hydroxyoct-1-enyl]-6-thiabicyclo[3.1.1]heptan-4-yl]hept-5-enoic acid Chemical compound OC(=O)CCC\C=C/C[C@@H]1[C@@H](/C=C/[C@H](O)CCCCC)C[C@@H]2S[C@H]1C2 OVGWMUWIRHGGJP-WVDJAODQSA-N 0.000 description 1
- 101710204139 Acyl carrier protein 2 Proteins 0.000 description 1
- 102100022734 Acyl carrier protein, mitochondrial Human genes 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 101100008649 Caenorhabditis elegans daf-5 gene Proteins 0.000 description 1
- 101100386238 Caenorhabditis elegans daf-8 gene Proteins 0.000 description 1
- 101710113789 Candidapepsin-2 Proteins 0.000 description 1
- 101710113783 Candidapepsin-3 Proteins 0.000 description 1
- 101000988961 Escherichia coli Heat-stable enterotoxin A2 Proteins 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 101000678845 Homo sapiens Acyl carrier protein, mitochondrial Proteins 0.000 description 1
- 101000611240 Homo sapiens Low molecular weight phosphotyrosine protein phosphatase Proteins 0.000 description 1
- 101710116852 Molybdenum cofactor sulfurase 1 Proteins 0.000 description 1
- 101100008641 Mus musculus Cd55b gene Proteins 0.000 description 1
- 229910014084 Na—B Inorganic materials 0.000 description 1
- 229910014130 Na—P Inorganic materials 0.000 description 1
- 229910014152 Na—P2 Inorganic materials 0.000 description 1
- 102100035703 Prostatic acid phosphatase Human genes 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 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
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052907 leucite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
-
- 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
-
- 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
- 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
- B01D53/9422—Processes characterised by a specific catalyst for removing nitrogen oxides by NOx storage or reduction by cyclic switching between lean and rich exhaust gases (LNT, NSC, NSR)
-
- 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
- B01D53/9431—Processes characterised by a specific device
-
- 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
- B01D53/9481—Catalyst preceded by an adsorption device without catalytic function for temporary storage of contaminants, e.g. during cold start
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—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
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/24—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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
- B01J29/52—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing iron group metals, noble metals or copper
- B01J29/56—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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789
- B01J29/61—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789 containing iron group metals, noble metals or copper
- B01J29/63—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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
- B01J29/68—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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J29/7676—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/783—CHA-type, e.g. Chabazite, LZ-218
-
- 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
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates (APO compounds)
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
-
- B01J35/30—
-
- B01J35/56—
-
- B01J35/617—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0246—Coatings comprising a 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/208—Hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
- B01D2253/1122—Metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/92—Dimensions
- B01D2255/9202—Linear dimensions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/018—Natural gas engines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
- B01D2258/0291—Flue gases from waste incineration plants
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- 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
- 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
- B01J29/7615—Zeolite Beta
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
A system for treating exhaust gas from a vehicular lean burn internal combustion engine with a lean/rich cycle comprises a NOx adsorber catalyst and a downstreamNH3-catalytic reduction (SCR) catalyst, wherein the NH3-SCR catalyst comprises copper supported on a molecular sieve, wherein the molecular serve (A) has a maximum ring size of 8 tetrahedral atoms; (D) is selected from the group consisting of aluminosilicate molecular sieves, metal substituted aluminosilicate molecular sieves and aluminophosphate molecular serves; and has a Framework Type Code selected from the group consisting of AEI, LEV, ERI, and DDR. The molecular sieve may have a silica to alumina ratio of 8 150 and may contain a total amount of copper of 0.5 5 weight percent. The NOx adsorber catalyst may comprise a precious metal and a basic metal selected from the group consisting of: an alkali metal; and alkaline earth metal; and a rare earth metal. A method for use with this system is also disclosed.
Description
SMALL PORE MOLECULAR SIEVE SUPPORTED COPPER CATALYSTS
DURABLE AGAINST LEAN/RICH AGING FOR THE REDUCTION OF NITROGEN
OXIDES
FIELD OF THE INVENTION
The present invention relates to small pore molecular sieve supported copper catalysts that are durable after being exposed to a reducing atmosphere, particularly after high temperature exposure.
BACKGROUND OF THE INVENTION
Selective catalytic reduction (SCR) of NOx by nitrogenous compounds, such as ammonia or urea, has developed for numerous applications including for treating industrial stationary applications, thermal power plants, gas turbines, coal-fired power plants, plant and refinery heaters and boilers in the chemical processing industry, furnaces, coke ovens, municipal waste plants and incinerators, and a number of vehicular (mobile) applications, e.g., for treating diesel exhaust gas.
Several chemical reactions occur in an NH3 SCR system, all of which represent desirable reactions that reduce NO to nitrogen. The dominant reaction is represented by reaction (1).
4NO+4NH+O2-*4N2+6I-l2O (1) Competing, non-selective reactions with oxygen can produce secondary emissions or may unproductivcly consume ammonia. One such non-selcctivc reaction is the complete oxidation of ammonia, shown in reaction (2).
4NH3 + 502 -* 4N0 + 6H20 (2) Also, side reactions may lead to undesirable products such as N20, as represented by reaction (3).
4NH -I-4NO + 302 -3 4N2O + 6H20 (3) Catalysts for SCR of NOx with NH3 may include, for example, aluminosilicate molecular sieves. One application is to control NO emissions from vehicular diesel engines, with the reductant obtainable from an ammonia precursor such as urea or by injecting ammoniaper Se.
To promote the catalytic activity, transition mctals may be incorporated into thc aluminosilicate molecular sieves. The most commonly tested transition metal molecular sieves are Cu/ZSM-5, Cu/Beta, Fe/ZSM-5 and Fe/Beta because they have a relatively wide temperature activity window. In general, however, Cu-based molecular sieve catalysts show better low temperature NO reduction activity than Fe-based molecular sieve catalysts.
In use, ZSM-5 and Beta molecular sieves have a number of drawbacks. They are susceptible to dealumination during high temperature hydrothermal ageing resulting in a loss of acidity, especially with Cu/Beta and Cu./ZSM-5 catalysts. Both beta-and ZSM-5-based catalysts are also affected by hydrocarbons which become adsorbed on the catalysts at relatively low temperatures and are oxidized as the temperature of the catalytic system is raised, generating a significant exotherm, which can thermally damage the catalyst. This problem is particularly acute in vehicular diesel applications where significant quantities of hydrocarbon can io be adsorbed on the catalyst during cold-start; and Beta and ZSM-5 molecular sieves are also prone to coking by hydrocarbons.
In general, Cu-based molecular sieve catalysts are less thermally durable, and produce higher levels of N20 than Fe-based molecular sieve catalysts. However, they have a desirable advantage in that they slip less ammonia in use compared with a corresponding Fe-molecular is sieve catalyst.
WO 2008/132452 discloses a method of converting nitrogen oxides in a gas to nitrogen by contacting the nitrogen oxides with a nitrogenous reducing agent in the presence of a zeolite catalyst containing at least one transition metal, wherein the zeolite is a small pore zeolite containing a maximum ring size of eight tetrahedral atoms, wherein the at least one transition metal is selected from the group consisting of Cr, Mn, Fe, Co, Ce, Ni, Cu, Zn, Ga, Mo, Ru, Rh, Pd, Ag, In, Sn, Re, Ir and Pt.
WO 2008/106518 discloses a combination of a fiber matrix wall flow filter and a hydrophobic chabazite molecular sieve as a SCR catalyst on the fiber matrix wall flow filter.
The filter purportedly achieves improved flexibility in system configuration and lower fuel costs for active regeneration. Such active regeneration would likely encompass exposure to lean atmospheric conditions. The reference, however, does not contemplate subjecting the filter to reducing conditions. The reference also fails to disclose or appreciate maintaining the durability of a catalyst after being exposed to such a reducing atmosphere.
SUMMARY OF THE INVENTION
According to one embodiment of the present invention, a method of using a catalyst comprises exposing a catalyst to at least one reactant in a chemical process. The catalyst comprises copper and a small pore molecular sieve having a maximum ring size of eight tetrahedral atoms. Preferably, the catalyst is a copper promoted small pore molecular sieve, i.e., a small pore molecular sieve loaded with copper. The chemical process undergoes at least one period of exposure to a reducing atmosphere. The catalyst has an initial activity and the catalyst has a final activity after the at least one period of exposure to the reducing atmosphere. The final activity is within 30% of the initial activity at a temperature between 200 and 500°C.
According to another embodiment of the present invention, a method of using a catalyst comprises exposing a catalyst to at least one reactant comprising nitrogen oxides in a chemical process comprising exhaust gas treatment. The catalyst comprises copper and a small pore molecular sieve having a maximum ring sizc of eight tctrahcdral atoms selected from thc group of Framework Type Codes consisting of CHA, LEY, EM and DDR. The chemical process undergoes at least one period of exposure to a reducing atmosphere. The catalyst has an initial activity, and the catalyst has a final activity after the at Icast one period of exposure to the reducing atmosphere. The final activity is within 10% of the initial activity at a temperature between 250 and 350°C.
BRIEF DESCRIPTION OF THE DRAWINGS
In order that the invention may be more fully understood, reference is made to the following drawing by way of illustration only, in which: Figure 1 is a graph illustrating NO conversion of medium pore and large pore molecular sieve supported copper catalysts after lean hydrothermal aging and leanrich cycle aging; Figure 2 is a graph illustrating NO conversion of Fe/molecular sieve catalysts after lean hydrothermal aging and Ican/rich cyclc aging; Figure 3 is a graph illustrating NOx conversion of small pore molecular sieve supported copper catalysts according to embodiments of the invention and a comparative Cu/Beta catalyst after lean hydrothermal aging and lean/rich cycle aging; and Figure 4 is a graph illustrating NO conversion efficiency over a NAC and combined NAC+SCR systems with different SCR catalysts according to embodiments of the invention and comparative examples.
DETAILED DESCRTPTION OF THE INVENTION
A method of treating NO in an exhaust gas of a lean bum internal combustion engine is to store the NO from a lean gas in a basic material and then to release the NO from the basic matcrial and rcducc it pcriodically using a rich gas. Thc combination of a basic matcrial (such as an alkali metal, alkaline earth metal or a rare earth metal), and a precious metal (such as platinum), and possibly also a rcduction catalyst component (such as rhodium) is typically referred to as a NOx adsorber catalyst NAC), a lean NOx trap (LNT), or a NO storage/reduction catalyst (NSRC). As used herein, NO storage/reduction catalyst, NO trap, and NOx adsorber catalyst (or their acronyms) may be used interchangeably.
Under certain conditions, during the periodically rich regeneration events, NH5 may be generated over a NO adsorber catalyst. The addition of a SCR catalyst downstream of the NO adsorber catalyst may improve the overall system NO reduction efficiency. In the combined system, the SCR catalyst is capable of storing the released NH3 from the NAC io catalyst during rich regeneration events and utilizes the stored NH3 to selectively reduce some or all of the NOx that slips through the NAC catalyst during the normal lean operation conditions. As used herein, such combined systems may be shown as a combination of their respective acronyms, e.g., NAC+SCR or LNT+SCR.
The combined NAC+SCR system imposes additional requirements on the 5CR catalyst is component. Namely, besides having good activity and excellent thermal stability, the 5CR catalyst has to be stable against lean/rich excursions. Such lean/rich excursions not only may occur during the regular NAC regeneration events, but also may happen during the NAC desulfation events. During the NAC desulfation events, the SCR catalyst may be exposed to temperatures much higher than it would be exposed to during the regular NOx regeneration events. Therefore, a good SCR catalyst that is suitable for the NAC+SCR systems needs to be durable after being exposed to a reducing atmosphere at high temperature. Although the present invention is described herein with particular emphasis on the SCR embodiment, it is contemplated that the present invention may encompass any catalysts which lose activity when exposed to a reducing atmosphere.
Catalysts are often unstable when exposed to a reducing atmosphere, more particularly a high temperature reducing atmosphere. For example, copper catalysts are unstable during repeated lean/rich high temperature excursions, e.g., as is often encountered in vehicle exhaust gas or an exhaust gas treatment system. The reducing atmosphere occurs in the rich phase of a lean/rich excursion cycle. The reducing atmosphere conditions, however, can occur in a variety of environments including but not limited to environments typical for the regeneration or the desulfation of a NOx adsorber catalyst, and for the active regeneration of a catalyzed soot filter, etc. Thus, as used herein, a reducing atmosphere is net reducing, for example, an exhaust gas having a lambda value of less than 1 (e.g., derived from an air/fuel ratio less than stoichiometric). Contrastingly, a non-reducing atmosphere is net oxidizing, e.g., having a lambda value greater than 1 (e.g., dcrivcd from an air/fricl ratio grcatcr than stoichiomctric).
Without wishing to be bound to a particular theory, it was believed prior to discovery of the present invention that molecular sieve supported copper catalysts would not maintain stability or activity when exposed to a reducing atmosphere (especially a reducing atmosphere encountered in a repeated lean/rich cycle excursions) because when exposed to the reducing atmosphere, the copper catalysts lost their activity. This loss of activity was suspected to be due to copper migration, sintcring, and/or reduced coppcr dispersion. Surprisingly, we io discovered in the present invention that small pore molecular sieve-supported copper catalysts maintained their catalytic activity even though the medium and large pore molecular sieve supported copper catalysts could not. It is believed that small pore molecular sieves provide a restriction on the copper from migrating out of the framework, sintering, losing copper dispersion, and beneficially resuhing in an improved stability and activity of the catalyst. The is medium and large pore molecular sieves, however, do not maintain their stability and activity when exposed to a reducing atmosphere possibly because of the effects of copper migration, sintering, and/or reduced copper dispersion.
According to one embodiment of the present invention, a method of using a catalyst comprises exposing a catalyst to at least one reactant in a chemical process. The catalyst comprises copper and a small pore molecular sieve having a maximum ring size of eight tetrahedral atoms. The chemical process undergoes at least one period of exposure to a reducing atmosphere. The catalyst has an initial activity and the catalyst has a final activity after the at least one period of exposure to the reducing atmosphere. The final activity is within 30% of the initial activity at a temperature between 150 and 650°C, preferably between 200 and 500°C.
A method of using a catalyst comprises exposing a catalyst to at least one reactant in a chemical process. As used herein, chemical process can include any suitable chemical process using a catalyst comprising a small pore molecular sieve comprising copper and encountering reducing conditions. Typical chemical processes include, but are not limited to, exhaust gas treatment such as selective catalytic reduction using nitrogenous reductants, lean NO catalyst, catalyzed soot filter, or a combination of any one of these with a NOx adsorber catalyst or a three-way catalyst (TWC), e.g., NAC+(downstream)SCR or TWC+(downstrcam)SCR.
According to another aspect of the invention, provided is a system comprising NAC+(downstream)SCR or TWC+(downstream)SCR, wherein the SCR catalyst comprises a copper promoted small pore zeolite sieve as described here.
According to another aspect of the invention, provided is an SCR catalyzed soot filter wherein the SCR catalyst comprises a copper promoted small pore zeolite sieve as described here.
A method of using a catalyst comprises exposing a catalyst to at least one reactant. The reactant may include any reactants typically encountered in the chemical processes above.
Reactants may include a selective catalytic reductant, such as ammonia. Selective catalytic io reduction may include (1) using ammonia or a nitrogenous reductant or (2) a hydrocarbon reductant (the latter also imown as lean NOx catalysis). Other reactants may include nitrogen oxides and oxygen.
The catalyst comprises a transition metal, preferably copper, and a small pore molecular sieve having a maximum ring size of eight tetrahedral atoms. As is used herein "molecular is sieve" is understood to mean a metastable material containing tiny pores of a precise and uniform size that may be used as an adsorbent for gases or liquids. The molecules which are small enough to pass through the pores are adsorbed while the larger molecules are not. The molecular sieve framework may be defined as is generally acceptable by the International Zeolite Association framework type codes (at http://www.iza-online.org/). These molecular sieves are described in more detail below.
Molecular sieves are typically defined by the member rings as follows: large pore rings are 12-member rings or larger; medium pore rings are 10-member rings; and small pore rings are 8-member rings or smaller. The catalyst in the present invention is a small pore ring having a maximum ring size of eight tetrahedral atoms.
Most catalysts are supported on medium pore (10-ring, such as ZSM-5) or large pore (12-ring, such as Beta) molecular sieves. A molecular sieve supported copper SCR catalyst, for example, may exhibit wide temperature windows under NO only conditions. These catalysts, however, are not stable against repeated lean/rich high temperature aging as is demonstrated in Figure 1. In Figure 1, a Cu/Beta catalyst (large pore) and a Cu/ZSM-5 catalyst (medium pore) are shown under hydrothermal aging conditions and lean/rich aging conditions. As is evidenced by the dotted lines representing the lean/rich aging conditions, these types of catalysts are not suitable when exposed to repeated reducing conditions. In particular, these catalysts are not suitable for NAC+SCR applications.
Molecular sieve supported iron SCR catalysts, although not as active as molecular sieve supported copper catalysts at low temperatures (e.g. <350°C), are stable against repeated lean/rich high temperature aging as shown in Figure 2. In Figure 2, Fe/Ferrierite, Fe/ZSM-5, and Fe/Beta are shown after hydrothermal aging and lean/rich aging conditions. Accordingly, molecular sieve supported iron catalysts have been the technology of choice due to their excellent stability against cycled lean/rich aging, e.g., as is encountered in NAC+SCR applications.
Small pore molecular sieve supported Cu catalysts have been demonstrated to exhibit improved NH3-SCR activity and excellent thermal stability. According to one aspect of the invention, it was found that this type of catalyst also tolerates repeated lean/rich high temperature aging. Figure 3 compares a series of small pore molecular sieve supported Cu catalysts (Cu/SAPO-34, Cu/Nu-3, and Cu/SSZ-13, respectively) against a comparative large is pore catalyst (Cu/Beta) after 700°C/2 hours hydrothermal aging and 6000(112 hours cycled leamrich aging, respectively. As is evident in Figure 3, the catalysts with small pore molecular sieve are very stable against leanlrich aging. In particular, the Cu/SAPO-34 catalyst exhibited exceptionally good low temperature activity and showed no activity degradation after cycled leanirich aging, i.e., repeated exposure to a reducing atmosphere.
The catalysts in embodiments of the present invention show a much wider temperature window of high NO conversion. The temperature range of improved conversion efficiency may range from about 150 to 650 °C, more particularly from 200 to 500°C, more particularly from 200 to 450°C, or most siiificantly from about 200 to 400°C. In these temperature ranges, conversion efficiencies after exposure to a reducing atmosphere, and even after exposure to a reducing atmosphere and to high temperatures (e.g., up to 850 o(') may range from greater than 55% to 100%, more preferably greater than 90% efficiency, and even more preferably greater than 95% efficiency. In particular, combined NAC+SCR systems show a much wider temperature window of high NO conversion compared to either NAC catalysts alone or NAC+SCR systems using a Fe/molecular sieve SCR catalyst. See Figure 4. For example at about 250°C and about 300°C, the NOx conversion efficiencies for systems subjected to lean/rich aging are as follows: System (undergone lean!rich aging) NOx Conversion % NOx Conversion at 250°C % at 300°C NAC alone 73 92 NAC + Fe/Beta SCR catalyst 87 90 NAC + Cu/SSZ-13 SCR catalyst 93 97 NAC + Cu/SAPO-34 SCR catalyst 97 96 As is evident from these results, the use of the NAC -I-Cu/small pore molecular sieve catalyst shows dramatic improvement in conversion efficiencies. These improvements are to the final NO emissions. Thus, an improvement from about 87% NOx conversion (about 13% NOx remaining) to about 97% NOx conversion (about 3% NO remaining) is about a 433% improvement in efficiency, based on the percent NO remaining.
The catalyst has an initial activity and the catalyst has a final activity after the at least one period of exposure to the reducing atmosphere. In certain embodiments, catalyst activity is NOx conversion efficiency. Accordingly, the initial activity is NOx conversion efficiency of a catalyst that has not been exposed to a reducing atmosphere and the final activity is NOx conversion efficiency of the catalyst after exposure to a reducing atmosphere. The initial activity may include a baseline aging under hydrothermal conditions. Hydrothermal conditions may include aging at 700°C for 2 hours with 5% H,O in aft.
The chemical process undergoes at least one period of exposure to a reducing atmosphere. The reducing atmosphere may include any suitable reducing atmosphere such as during rich conditions in a lean/rich aging cycle. For example, a localized reducing atmosphere may also occur during catalyzed soot filter regeneration. The at least one period of exposure may include repeated exposures to reducing conditions or a prolonged exposure to reducing conditions. For example, a repeated exposure may include a cycled lean'rich aging at 600°C for 12 hours. A lean cycle may last from 15 seconds to several tens of minutes, and a rich cycle may last from less than I second to several minutes. In a NAC-SCR system or TWC-SCR system, the rich cycle may range, for example, from 1 to 60 continuous seconds, from I to 15 continuous seconds, or from 5 to 15 continuous seconds. In a coated soot filter application (e.g., a SCRIDPF (diesel particulate filter), the rich cycle may range, for example, from 30 seconds to 60 minutes of continuous exposure, from 5 minutes to 30 minutes of continuous exposure, or from 10 minutes to 30 minutes of continuous exposure. For example, the lean portion of the cycle may consist of exposure to 200 ppm NO, 10% 02, 5% 1-120, 5% CO2 in N2, and thc rich portion of the cycle may consist of cxposure to 200 ppm NO, 5000 ppm C3H6, 1.3% H2, 4% CO. 1% 02, 5% H20, 5% CO2 inN2. The reducing atmosphere maybe a high temperature reducing atmosphere. A high temperature reducing atmosphere may occur at a temperature from about 150°C to 850°C or more particularly from about 450°C to 850°C.
The final activity is within about 30%, more preferably within about 10%, more preferably within about 5%, even more preferably within about 3% of the initial activity at a catalytic operating temperature. Preferably, the catalytic operating temperature is between io about 150 and about 650 "C and more preferably between about 200 and about 500°C. While the activity of the catalyst is preferably measured within a temperature range of 200 and 500°C, portions of the chemical process can operate at any temperature, for example, a wider temperature range including higher temperatures. For example, catalyst activity will still be maintained in the temperature range of 200 and 500°C even after the catalyst has been exposed is to higher temperatures, e.g. up to 850 °C. As used herein, when the final activity is given as a percentage of the initial activity, it is given as an average of percentages over the temperature range provided; in other words, if a final activity is said to be within 30% of the initial activity at a temperature between 200 and 500°C, it need not be less than 30% at every temperatures tested in that range, but would merely average less than 30% over the temperatures tested.
Moreover, while activity is identified as N0 conversion in the examples of this application, the activity could be some other measure of catalyst activity depending on the chemical process, as is known in the art. The data showing catalyst activity and the percentage of initial activity to final activity is evidenced in the following tables (See also Figure 3). A negative number means that the activity after exposure to the reducing conditions actually improved relative to the initial activity (and therefore would certainly be "within" a certain positive percentage of the initial activity): -10-For the embodiment using Cu/Nu-3 the following data was obtained: TEMP UT Aging TEMP LRAging % 9 150 9 -2% 50 198 52 -2% 250 76 250 75 1% 350 72 350 69 4% 450 62 450 58 6% 550 45 550 43 3% 650 27 650 26 2% Thus, the lean/rich aging % NO reduction was within about 6% of the hydrothermal aging % NO reduction. Accordingly, the catalyst remained stable and had good activity following repeated exposure to reducing conditions throughout the temperature ranging from about 150 to about 650°C.
For the embodiment using Cu/S SZ-13 the following data was obtained: TEMP FIT Aging TEMP LRAging 164 61 160 19 68% 218 100 216 71 29% 269 100 269 97 3% 373 97 372 86 12% 473 86 474 68 20% 572 64 573 41 36% 668 22 669 -7 134% Thus, the lean/rich aging % NO> reduction was within about 30% of the hydrothermal io aging % NO reduction throughout the temperature ranging from about 200 to about 500°C.
For the embodiment using Cu/SAPO34 the following data was obtained: TEMP FIT Aging TEMP LRAging 156 33 156 47 -41% 211 95 212 97 -3% 264 99 265 99 0.04% -Il-TEMP HT Aging TEMP LR Aging 366 89 366 89 -0.01% 464 86 465 83 3% 561 70 564 62 11% 658 34 662 26 22% Thus, the lean/rich aging % NO reduction was within about 3% of the hydrothermal aging % NO reduction throughout the temperature ranging from about 200 to about 500°C, and within about 10% at temperatures ranging from about 200 to 560°C.
As a comparative example a Cu/Beta, large pore molecular sieve catalyst, was compared: TEMP HT Aging TEMP LR Aging % 21 152 9 57% 72 199 24 67% 250 93 250 30 67% 350 93 351 26 72% 450 82 450 37 56% 550 82 550 54 35% 650 64 650 49 24% The Cu/Beta comparative example showed poor activity following lean/rich cycled aging. Thus, exposure to a reducing atmosphere for the copper molecular sieve catalysts causes poor stability and activity as was contemplated prior to discovery of the present invention.
io According to one embodiment of the present invention, a method of using a catalyst comprises exposing a catalyst to at least one reactant comprising nitrogen oxides in a chemical process comprising exhaust gas treatment. The catalyst comprises copper and a small pore molecular sieve having a maximum ring size of eight tetrahedral atoms selected from the group of Framework Type Codes consisting of CHA, LEY, EM and DDR. The chemical process is undergoes at least one period of exposure to a reducing atmosphere. The catalyst has an initial activity, and the catalyst has a final activity after the at least one period of exposure to the reducing atmosphere. The final activity is within 10% of the initial activity at a temperature between 250 and 350°C. In a preferred embodiment, the catalyst has a final activity that is within 3% of the initial activity at a temperature between 250 and 350°C. -12-
In an embodiment of the invention, the catalysts have been combined with a NAC (NOx adsorber catalyst) and tested as NAC+SCR systems. Figure 4 compares the NO reduction efficiency over a NAC alone and NAC+SCR systems with different SCR small pore molecular sieve catalysts (Cu/SAPO-34, and Cu/SSZ-13), and a comparative example of a Fe/beta catalyst. Combining an Fe/molecular sieve SCR with a NAC catalyst has been shown to improve the system NOx conversion compared to NAC alone. Remarkably, however, the other two systems with a small pore molecular sieve comprising copper, i.e., Cu/SAPO-34 or Cu/SSZ-l3, also exhibited further improved NO removal efficiency. This is especially evident at low temperatures (2OO-35OC). These results clearly suggest that small pore molecular sieve supported Cu catalysts offers new potential to thrther improve the performance of NAC+SCR systems.
In addition to NAC+SCR applications, the small pore molecular sieve supported Cu catalysts offer significant performance advantages for other applications that may be exposed to a high temperature reducing atmosphere. For example, a small pore molecular sieve supported is Cu catalyst may be used in a reducing atmosphere which occurs during active regeneration of a SCRJDPF (diesel particulate filter). Small pore molecular sieve supported Cu catalysts provide excellent thermal durability and exceptional stability against reducing conditions, e.g., rich aging that occurs in exhaust gas treatment systems.
It will be appreciated that by defining the molecular sieve by their Framework Type Codes we intend to include the "Type Material" and any and all isotypic framework materials.
(The "Type Material" is the species first used to establish the framework type). Reference is made to Table l,which lists a range of illustrative molecular sieve materials for usc in the present invention. For the avoidance of doubt, unless otherwise made clear, reference herein to a molecular sieve by name, e.g. "chabazite", is to the molecular sieve material per se (in this example the naturally occurring type material chabazite) and not to any other material designated by the Framework Type Code to which the individual molecular sieve may belong, e.g. some other isotypic framework material. Use of a FTC herein is intended to refer to the Type Material and all isotypic framework materials defined by that FTC.
The distinction between molecular sieve type materials, such as naturally occurring (i.e. mineral) chabazite, and isotypes within the same Framework Type Code is not merely arbitrary, but reflects differences in the properties between the materials, which may in turn lead to differences in activity in the method of the present invention. It will be appreciated, e.g. from -13-Table I hereinbelow, that by "MeAPSO" and "MeAIPO" we intend zeotypes substituted with one or more metals. Suitable substituent metals include one or more of without limitation, As, B, Be, Co, Fe, Ga, Ge, Li, Mg, Mn, Zn and Zr.
In a particular embodiment, the small pore molecular sieve catalysts for use in the present invention can be selected from the group consisting of aluminosilicate molecular sieves, metal-substituted aluminosilicate molecular sieves and aluminophosphate molecular sieves.
Aluminophosphate molecular sieves with application in the present invention include aluminophosphate (AIPO) molecular sieves, metal substituted (MeAIPO) molecular sieves, silico-aluminophosphatc (SAPO) molecular sicvcs and metal substituted silico-aluminophosphate (MeAPSO) molecular sieves.
In one embodiment, the small pore molecular sieve is selected from the group of Framework Type Codes consisting of: ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB, EDT, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, KEI, MER, MON, N5I, OWE, PAU. PHI, RHO, RTH, SAT, SAY, STY, THO, TSC, IJET, UFI, is VNI,YIJGandZON.
In an embodiment, the small pore molecular sieve containing a maximum ring size of eight tetrahedral atoms is selected from the group of Framework Type Codes consisting of CEIA, LEV, ERI, and DDR. In a preferred embodiment, the small pore molecular sieve comprises a CHA Framework Type Code selected from SAPO-34 or SSZ-l3. In another embodiment, the small pore molecular sieve comprises a LEY Framework Type Code Nu-3.
Additionally, the small pore molecular sieve may comprise an AEI Framework Type Code SAPO-18, an ERI Framework Type Code ZSM-34, and/or a DDR Framework Type Code siwna-T. The small pore molecular sieve may also include disordered molecular sieves, such as an intergrown or mixed phase AEIICHA, AEI/SAY, etc. Molecular sieves with application in the present invention can include those that have been treated to improve hydrothermal stability. Illustrative methods of improving hydrothermal stability include: (I) Dealumination by: steaming and acid extraction using an acid or complexing agent e.g. (EDTA -ethylenediaminetetracetic acid); treatment with acid and/or complexing agent; treatment with a gaseous stream of SiCI4 (replaces Al in the molecular sieve framework with Si); (ii) Cation exchange -usc of multi-valcnt cations such as La; and -14- (iii) Use of phosphorous containing compounds (see e.g. U.S. Patent No. 5,958,818).
Illustrative examples of suitable small porc molecular sieves arc set out in Table 1.
Table 1: Small Pore Molecular Sieve Molecular Type material* and Dimension-Pore size (A) Additional Sieve illustrative isotypic ality info Framework framework Type (by structures Framework Type_Code) ______________________ _____________ ________________ ____________ ACO *ACP1 3D 3.5 x 2.8, 3.5 x Ring sizes - ____________ _________________ __________ 3.5 8,4 AEI *AlpO_1 8 3D 3.8 x 3.8 Ring sizes - ______________ ___________________ ____________ _______________ 8,6,4 _____________ [Co-A1-P-O]-AEI ___________ ______________ __________ __________ SAPO-18 _________ ___________ ________ ______________ SIZ-8 ____________ _______________ ___________ ______________ SSZ-39 ____________ _______________ ___________ AEN AIPO-EN3 2D 4.3 x 3.1, 2.7 x Ring sizes - ___________ ________________ _________ 5.0 8,6,4 _____________ AIPO-53(A) ___________ ______________ __________ _____________ AIPO-53(B) ___________ ______________ __________ ___________ [Ga-P-OI-AEN _________ ___________ ________ ______________ CFSAPO-1 A ____________ _______________ ___________ ______________ CoIST-2 ____________ _______________ ___________ ______________ IST-2 ____________ _______________ ___________ _____________ JDF-2 ___________ ______________ __________ ___________ MCS-1 _________ ____________ _________ __________ MnAPO-14 _________ ___________ ________ ______________ Mu-10 ____________ _______________ ___________ ______________ UiO-12-500 ____________ _______________ ___________ ______________ UiO-12-as ____________ _______________ ___________ kFN tAIPO-14 3D 1.9x4.6,2.1 x Ringsizes- ____________ ________________ __________ 4.c,3.3x4.0 8,6,4 I(C3N2U2)-[Mn-Al-P- __________ O]-AFN _________ ___________ ________ _____________ GaPO-14 ___________ ______________ __________ AFT *A1p052 3D 3.8 x 3.2, 3.8 x Ring sizes - ___________ ________________ _________ 3.6 8,6,4 AFX *SAPO56 3D 3.4 x 3.6 Ring sizes - ______________ ____________________ ____________ _______________ 8, 6, 4 MAPSO-56, M=Co, ____________ Mn, Zr __________ ____________ _________ ______________ SSZ-16 ____________ _______________ ___________ ANA tAnalcime 3D 4.2 x 1.6 Ring sizes - ______________ ____________________ ____________ _______________ 8, 6, 4 _______________ AIPO4-pollucite _____________ ________________ ____________ -15-Molecular Type material* and Dimension-Pore size (A) Additional Sieve illustrative isotypic ality info Framework framework Type (by structures Framework Type_Code) ______________________ _____________ ________________ ____________ _____________ MPO-24 ___________ ______________ __________ Ammonioleucite ____________ [A1-Co-P-0]-ANA __________ ____________ _________ _____________ [A1-Si-P-0]-ANA ___________ ______________ __________ ___________ Cs-I[A1-Ge-0]-ANA _________ ___________ ________ ______________ Cs-[Bc-Si-0]-ANA ____________ _______________ ___________ I Cs16 I [Cug S 140096]-
__________ ANA _________ ___________ ________
______________ ICs-FeI[Si-OI-ANA ____________ _______________ ___________ Cs-Na-(H20)I [Ga-Si- __________ 01-ISA _________ ___________ ________ __________ [Ga-Gc-0]-ANA _________ ___________ ________ ___________ K-I[B-Si-0]-ANA _________ ___________ ________ ___________ IKH[Be-B-P-01-ANA _________ ____________ _________ Li-[Li-Zn-Si-0]-
__________ ISA _________ ___________ ________
_____________ I Li-Na [Al-Si-0]-ANA ___________ ______________ __________ INa-I[Be-B-P-0]-
__________ ISA _________ ___________ ________
(NH4-[Be-B-P-0]-
___________ ANA _________ ___________ ________
(NH4)-[Zn-Ga-P-0]-
__________ ISA _________ ___________ ________
___________ [Zn-As-0]-ANA _________ ___________ ________ __________ Ca-D _________ ___________ ________ _________________ Hsianghualite ______________ __________________ _____________ __________________ Leucite _______________ ___________________ ______________ ____________ Na-B __________ ____________ _________ _________________ Pollucite ______________ __________________ _____________ __________________ Wairakite _______________ ___________________ ______________ APC 4AIPO-C 2D 3.7 x 3.4, 4.7 x Ring sizes - ___________ ________________ _________ 2.0 8,6,4 ____________ AIPO-I-13 __________ ____________ _________ ___________ CoAPO-H3 _________ ____________ _________ APD 4AIPO-D 2D 6.0 x 2.3, 5.8 x Ring sizes - ___________ ________________ _________ 1.3 8,6,4 ____________ APO-CJ3 __________ ____________ _________ ATT tA1PO-12-TAM[J 2D 4.6x4.2,3.8x Ringsizes- ____________ ________________ __________ 3.8 8,6,4 ______________ AIPO-33 ____________ _______________ ___________ ___________ RMA-3 _________ ___________ ________ -16-Molecular Type material* and Dimension-Pore size (A) Additional Sieve illustrative isotypic ality info Framework framework Type (by structures Framework Type_Code) ______________________ _____________ ________________ ____________ CDO CDS..1 2D 4.7 x 3.1,4.2 x Ring sizes - ____________ ________________ __________ 2.5 8,5 _______________ MC M-65 _____________ ________________ ____________ ____________ IJZM-25 __________ ____________ _________ CFIA *Chabazite 3D 3.8 x 3.8 Ring sizes - ______________ ___________________ ____________ _______________ 8,6,4 _____________ A1PO-34 ___________ ______________ __________ __________ [A1-As-O]-CHA _________ ___________ ________ ___________ [Al-Co-P-rn-ciA _________ ____________ _________ ___________ ICol_[Be-P-O]-CHA _________ ___________ ________ Co3 (C5N4H24)3 (H2O)Q [Be18P18O72]-
__________ CHA _________ ___________ ________
___________ [Co-A1-P-O]-CHA _________ ____________ _________ Li-Nal [A1-Si-O]- ___________ Cl-IA _________ ____________ _________ ___________ [Mg-A1-P-O]-CHA _________ ___________ ________ ____________ [Si-O]-CHA __________ ____________ _________ ____________ [Zn-A1-P-O]-CHA __________ ____________ _________ ____________ [Zn-As-O]-CHA __________ ____________ _________ ___________ CoAPO-44 _________ ____________ _________ ___________ CoAPO-47 _________ ____________ _________ ___________ DAF-5 _________ ____________ _________ ______________ GaPO-34 ____________ _______________ ___________ _______________ IC-Chabazite _____________ ________________ ____________ ____________ Linde D __________ _____________ _________ _____________ Linde_R ___________ ______________ __________ ____________ LZ-218 __________ ____________ _________ ___________ MeAPO-47 _________ ___________ ________ _____________ MeAPSO-47 ___________ ______________ __________ _________________ (Ni(deta)2)-UT-6 ______________ __________________ _____________ ______________ Phi ____________ _______________ ___________ ___________ SAPO-34 _________ ___________ ________ ___________ SAPO-47 _________ ___________ ________ ______________ SSZ-13 ____________ _______________ ___________ __________ UiO-21 ________ __________ _______ _______________ Wilihendersonite _____________ ________________ ____________ ____________ ZK-14 __________ ____________ _________ ____________ ZYT-6 __________ ____________ _________ DDR *Decadodecasil 3R 2D 4.4 x 3.6 Ring sizes - ______________ ____________________ ____________ _______________ 8, 6, 5, 4 -17-Molecular Type material* and Dimension-Pore size (A) Additional Sieve illustrative isotypic ality info Framework framework Type (by structures Framework Type_Code) ______________________ _____________ ________________ ____________ ___________ [B-Si-O]-DDR _________ ___________ ________ ______________ Sigma-i ____________ _______________ ___________ ___________ ZSM-58 _________ ____________ _________ DFT *DAF2 3D 4.i x4.i,4.7x Ringsizes- _____________ __________________ ___________ 1.8 8,6,4 ACP-3, [Co-A1-P-O]-
___________ DFT _________ ___________ ________
____________ [Fe-Zn-P-O]-DFT __________ _____________ _________ ____________ [Zn-Co-P-O]-DFT __________ ____________ _________ ___________ UCSB-3GaGe _________ ____________ _________ ___________ UCSB-3ZnAs _________ ____________ _________ UiO-20, [Mg-P-O]-
___________ DFT _________ ____________ _________
EAB *TMKE 2D 5.i x3.7 Ring sizes- ______________ ____________________ ____________ _______________ 8, 6, 4 _________________ Beilbergite ______________ __________________ _____________ EDT *Edingtonite 3D 2.8 x 3.8, 3.1 x Ring sizes - ___________ ________________ _________ 2.0 8,4 I(C3H12N2)2.51 ______________ [Zn5P5O20J-EDI ____________ _______________ ___________ ____________ [Co-A1-P-Oj-EDT __________ ____________ _________ ____________ [Co-Ga-P-Oj-EDI __________ ____________ _________ ______________ Li-[A1-Si-O]-EDI ____________ _______________ ___________ Rb7 Na (H2O)3 _______________ [GaMSil 2040] -EDT _____________ ________________ ____________ ____________ [Zn-As-O]-EDI __________ ____________ _________
__________ K-F _________ ___________ ________
______________ Linde_F ____________ _______________ ___________ ______________ Zeolite_N ____________ _______________ ___________ Eli *Epistilbite 2D 4.5 x 3.7, 3.6 x Ring sizes - ___________ ________________ _________ 3.6 8,4 EKE *Erionite 3D 3.6 x 5.1 Ring sizes - ______________ ___________________ ____________ _______________ 8,6,4 ____________ A1PO-i7 __________ _____________ _________ ______________ Linde_T ____________ _______________ ___________ ____________ LZ-220 __________ ____________ _________ __________ SAPO-17 _________ ___________ ________ ____________ ZSM-34 __________ ____________ _________ GIS *Gismondine 3D 4.5 x 3.1,4.8 x Ring sizes - ___________ ________________ _________ 2.8 8,4 __________________ Amicite _______________ ___________________ ______________ -18-Molecular Type material* and Dimension-Pore size (A) Additional Sieve illustrative isotypic ality info Framework framework Type (by structures Framework Type_Code) ______________________ _____________ ________________ ____________ ____________ [Al-Co-P-0]-GTS __________ _____________ _________ ______________ [A1-Ge-0]-GIS ____________ _______________ ___________ ____________ [A1-P-0]-GIS __________ _____________ _________ _____________ [Be-P-0I-GIS ___________ ______________ __________ _______________ [Be5P5O37]-GIS _____________ ________________ ____________ ______________ [Zn8P8O32]-GIS ____________ _______________ ___________ _____________ [Co-A1-P-0]-GIS ___________ ______________ __________ _____________ [Co-Ga-P-0]-GIS ___________ ______________ __________ _____________ [Co-P-O]-GIS ___________ ______________ __________ ______________ ICs4[Zn4B4PM02I-0IS ____________ _______________ ___________ ______________ [Ga-Si-0]-GTS ____________ _______________ ___________ ______________ [Mg-A1-P-0]-GIS ____________ _______________ ___________ (N U4)4[Zn4B4P8032]-
__________ GIS ________ __________ _______
_______________ IRb4[Zn4B4Ps032I-GIS _____________ ________________ ____________ ______________ [Zn-Al-As-0j-Gl S ____________ _______________ ___________ _____________ [Zn-Co-B-P-O]-GIS ___________ ______________ __________ ____________ [Zn-Ga-As-0]-GIS __________ ____________ _________ _____________ [Zn-Ga-P-0] -GIS ___________ ______________ __________ _______________ Garronite _____________ ________________ ____________ ______________ Gobbinsite ____________ _______________ ___________ ___________ MAPO-43 _________ ___________ ________ ___________ MAPSO-43 _________ ___________ ________ _____________ Na-P 1 ___________ ______________ __________ ______________ Na-P2 ____________ _______________ ___________ ___________ SAPO-43 _________ ___________ ________ ______________ TMA-gisniondinc ____________ _______________ ___________ 000 *000sccreekitc 3D 2.8 x 4.0, 2.7 x Ring sizes - ____________ _________________ __________ 4.I,4.7x2.9 8,6,4 IHW *lTQ32 2D 3.5 x 4.3 Ring sizes - ______________ ____________________ ____________ _______________ 8, 6, 5, 4 ITE *ITQ..3 2D 4.3 x 3.8, 2.7 x Ring sizes - ____________ ________________ __________ 5.8 8,6,5,4 ______________ Mu-i 4 ____________ _______________ ___________ ______________ SSZ-36 ____________ _______________ ___________ ITW *lTQ1 2 2D 5.4 x 2.4, 3.9 x Ring sizes - ___________ ________________ _________ 4.2 8,6,5,4 LEV *Leyyne 2D 3.6 x 4.8 Ring sizes - ______________ ____________________ ____________ _______________ 8, 6, 4 -19-Molecular Type material* and Dimension-Pore size (A) Additional Sieve illustrative isotypic ality info Framework framework Type (by structures Framework Type_Code) ______________________ _____________ ________________ ____________ ____________ AIPO-35 __________ _____________ _________ ____________ CoDAF-4 __________ ____________ _________ ___________ LZ-132 _________ ____________ _________ __________ NU-3 ________ __________ _______ ___________ RUB-i [B-Si-O]-LEV _________ ___________ ________ ___________ SAPO-35 _________ ___________ ________ ____________ ZK-20 __________ ____________ _________ ___________ ZnAPO-35 _________ ____________ _________ IC! ZK-5 3D 3.9 x 3.9 Ring sizes - ______________ ____________________ ____________ _______________ 8, 6, 4 1 8-crown-6 [Al-Si- __________ O]-KFI _________ ___________ ________ _____________ [Zn-Ga-As-O]-KFI ___________ ______________ __________ __________________ (Cs,K)-ZK-5 _______________ ___________________ ______________
_________________ P ______________ __________________ _____________
___________ Q _________ ____________ _________
MER *Mcrljnoite 3D 3.5 x 3.1, 3.6 x Ring sizes - 2.7,5.1 x3.4, 8,4 _______________ ______________________ _____________ 3.3 x_3.3 ____________ ___________ [A1-Co-P-O]-MER _________ ____________ _________ ______________ Ba-[A1-Si-O]-MER ____________ _______________ ___________ IBa-C1-I[A1-Si-O]-
____________ M ER __________ ____________ _________
____________ [Ga-A1-Si-O]-MER __________ _____________ _________ ____________ IK-H[Al-Si-OI-MER __________ _____________ _________ ___________ NH4-[Be-P-O]-MER _________ ___________ ________
__________ K-M ________ __________ _______
____________ Linde W __________ _____________ _________ _________________ Zeolite_W ______________ __________________ _____________ MON 2D 4.4 x 3.2, 3.6 x Ring sizes - ___________ _______________ _________ 3.6 8,5,4 __________ A1-Ge-O]-MON ________ __________ _______ NSI tNu-6(2) 2D 2.6 x 4.5, 2A x Ring sizes - ____________ ________________ __________ 4.8 8,6,5 _____________ EIJ-20 ___________ ______________ __________ OWE *UiO28 2D 4.0 x 3.5, 4.8 x Ring sizes - ___________ _______________ _________ 3.2 8,6,4 ___________ ACP-2 _________ ____________ _________ PAU tPaulingite 3D 3.6 x 3.6 Ring sizes - ______________ ____________________ ____________ _______________ 8, 6, 4 ______________ [Ga-Si-O]-PAU ____________ _______________ ___________ -20 -Molecular Type material* and Dimension-Pore size (A) Additional Sieve illustrative isotypic ality info Framework framework Type (by structures Framework Type_Code) ______________________ _____________ ________________ ____________ ___________ ECR-18 _________ ___________ ________ PHI *phjfljpsjte 3D 3.8 x 3.8, 3.0 x Ring sizes - ____________ _________________ __________ 4.3,3.3x3.2 8,4 ______________ [A1-Co-P-O]-P I-li ____________ _______________ ___________ ___________ DAF-8 _________ ____________ _________ ______________ Flarmotome ____________ _______________ ___________ _______________ Welisite _____________ ________________ ____________ ____________ ZK-19 __________ ____________ _________ RHO *pJw 3D 3.6 x 3.6 Ring sizes - ______________ ____________________ ____________ _______________ 8, 6, 4 ___________ [Be-As-O]-RHO _________ ___________ ________ ___________ [Bc-P-OI-RHO _________ ___________ ________ ___________ [Co-AI-P-OI-RHO _________ ___________ ________ ____________ IHH[A1-S i-O]-RHO __________ ____________ _________ ____________ [Mg-A1-P-O]-RI-IO __________ ____________ _________ ___________ [Mn-AI-P-0]-RHO _________ ___________ ________ Na15 Cs3 _______________ [AI24Ge,40q5]-RHO _____________ ________________ ____________ ______________ INH4-[A1-Si-O]-RHO ____________ _______________ ___________ ___________ Rb-[Be-As-O] -RHO _________ ___________ ________ _______________ Gallo silicate_ECR-10 _____________ ________________ ____________ ____________ LZ-214 __________ ____________ _________ _______________ Pahasapaite _____________ ________________ ____________ RTH tRUB-13 2D 4.1 x3.8,5.6x Ring sizes- ___________ ________________ _________ 2.5 8,6,5,4 ______________ SSZ-36 ____________ _______________ ___________ ______________ SSZ-50 ____________ _______________ ___________ SAT *STA2 3D 5.5 x 3.0 Ring sizes - ______________ ____________________ ____________ _______________ 8, 6, 4 SAY *MgSTA7 3D 3.8 x 3.8, 3.9 x Ring sizes - ___________ _______________ _________ 3.9 8,6,4 ____________ Co-STA-7 __________ ____________ _________ ____________ Zn-STA-7 __________ _____________ _________ SBN *UCSB9 3D TBC Ring sizes - _______________ ______________________ _____________ ________________ 8, 4, 3 ______________ SU-46 ____________ _______________ ___________ Sly *51Z7 3D 3.5x3.9,3.7x Ringsizes- _____________ __________________ ___________ 3.8,3.8x3.9 8,4 THO tThomsonite 3D 2.3 x 3.9, 4.0 x Ring sizes - _____________ __________________ ___________ 2.2, 3.0 x 2.2 8,4 ___________ [AI-Co-P-0]-THO _________ ____________ _________ -21 -Molecular Type material* and Dimension-Pore size (A) Additional Sieve illustrative isotypic ality info Framework framework Type (by structures Framework Type_Code) ______________________ _____________ ________________ ____________ ____________ [Ga-Co-P-O]-THO __________ ____________ _________ Rb201[Ga2oGc2oO8o]-
___________ THO _________ ___________ ________
___________ [Zn-AI-As-O]-THO _________ ____________ _________ ____________ [Zn-P-OI-THO __________ ____________ _________ ____________ [Ga-Si-Oj-THO) __________ ____________ _________ ____________ [Zn-Co-P-O]-THO __________ ____________ _________ TSC *Tsehortnerite 3D 4.2 x 4.2, 5.6 x Ring sizes - ____________ ________________ __________ 3.1 8,6,4 UEI *Mul8 2D 3.5 x 4.6, 3.6 x Ring sizes - ___________ ________________ _________ 2.5 8,6,4 UFI tUZM-5 2D 3.6 x 4.4, 3.2 x Ring sizes - ____________ _________________ __________ 3.2 (cage) 8,6,4 \TNJ tVPJ-9 3D 3.5 x 3.6, 3.1 x Ring sizes - ____________ _________________ __________ 4.0 8,5,4,3 YUG *yugawaralite 2D 2.8 x 3.6, 3.1 x Ring sizes - ____________ ________________ __________ 5.0 8,5,4 ___________ Sr-Q _________ ___________ ________ ZON *zApoM I 2D 2.5 x 5.1,3.7 x Ring sizes - ___________ _______________ _________ 4A 8,6,4 __________ GaPO-DAB-2 _________ ___________ ________ __________ lJiO-7 _________ ___________ ________ Small pore molecular sieves with particular application for exposure to reducing conditions are set out in Table 2.
Table 2: Preferred Small Pore Molecular Sieves.
Structure Molecular Sieve CHA SAPO-34 _____________ AIPO-34 _____________ SSZ-13 LEV Levynite ________________ Nu-3 ___________ LZ-132 __________ SAPO-35 ____________ ZK-20 Em Erionite ___________ ZSM-34 _____________ Linde type T DDR Deca-dodecasil 3R -22 -Structure Molecular Sieve _____________ Sigma-I KR ZlC-5 I 8-crown-6 ______________ [Zn-Ga-As-O]-KFI
EAB TMA-E
PAU ECR-18 MER Medinoite AR SSZ-39 _____________ SAPO-1 8 GOO Goosecreekite YUG Yugawaralite GIS P1 YNI VPI-9 Molecular sieves for use in the present application include natural and synthetic molecular sieves, preferably synthetic molecular sieves because the molecular sieves can have a more uniform: silica-to-alumina ratio (SAR), crystallite size, crystallite morphology, and the absence of impurities (e.g. alkaline earth metals). Small pore aluminosilicate molecular sieves may have a silica-to-alumina ratio (SAR) of from 2 to 300, optionally 4 to 200, and preferably 8 to 150. It will be appreciated that higher SAR ratios are prefened to improve thermal stability but this may negatively affect transition metal exchange.
The at least one reactant may contact the catalyst at a gas hourly space velocity of from 5,000 hf' to 500,000 hf', optionally from 10,000 hr" to 200,000 hr1.
Small pore molecular sieves for use in the invention may have three-dimensional dimensionality, i.e. a pore structure which is interconnected in all three crystallographic dimensions, or two-dimensional dimensionality. In one embodiment, the small pore molecular is sieves for use in the present invention consist of molecular sieves having three-dimensional dimcnsionality. In another embodiment, the small pore molecular sieves for use in the present invention consist of molecular sieves having two-dimensional dimensionality.
In certain embodiments, the small pore molecular sieve comprises, consists essentially of, or consists of a disordered framework selected from the group consisting of ABC-6, AET/CHA, AEI/SAV, AEN/UEI, AFSIBPH, BEC/ISY, beta, friajasite, ITE/RTH, KFI/SAV, lovdarite, montesommaite, MTT/TON, pentasils, SBS/SBT, SSF/STF, SSZ-33, and ZSM-48.
In a preferred embodiment, one or more of the small pore molecular sieves may comprise a CHA Framework Type Code selected from SAPO-34, AIPO-34, SAPO-47, ZYT-6, CAL-i, -23 -SAPO-40, SSZ-62 or SSZ-13 and/or an AEI Framework Type Code of selected from A1PO-IS, SAPO-18, SIZ-8, or SSZ-39. In one embodiment, the mixed phase composition is an AEI/CHA-mixcd phase composition. The ratio of each framework type in the molecular sieve is not particularly limited. For example, the ratio of AEI/CHA may range from about 5/95 to about 95/5, preferably about 60/40 to 40/60. In an exemplary embodiment, the ratio of AEI/CHA may range from about 5/95 to about 40/60. It is envisioned that a disordered molecular sieve, such as AEI/CHA, will be used as the support for one or more transition metals, such as Cr, Mn, Fe, Co, Ce, Ni, Cu, Zn, Ga, Mo, Ru, Rh, Pd, Ag, In, Sn, Re, Ir, Pt, and mixtures thereof, preferably Cr, Mn, Fe, Co, Cc, Ni, Cu, Rh, Pd, Pt, and mixtures thereof, more io preferably Fe and/or Cu, and most preferably copper.
The total of the copper metal that can be included in the molecular sieve can be from 0.01 to 20 wt%, based on the total weight of the catalyst. In one embodiment, the total of the copper that can be included can be from 0.1 to 10 wt%. In a particular embodiment, the total of is copper that can be included is from 0.5 to 5 wt%. The copper may be included in the molecular sieve by any feasible method. For example, it can be added after the molecular sieve has been synthesized, e.g. by incipient wetness or exchange process; or can be added during molecular sieve synthesis.
A preferred two dimensional small pore molecular sieve for use in the present invention consists of Cu/LEY, such as Cu/Nu-3, whereas a preferred copper-containing three dimensional small pore molecular sieve/aluminophosphate molecular sieve for use in the present invention consists of Cu/CHA, such as Cu/SAPO-34 or Cu/SSZ-13.
The molecular sieve catalysts for use in the present invention can be coated on a suitable substrate monolith or can be formed as extruded-type catalysts, but are preferably used in a catalyst coating. In one embodiment, the molecular sieve catalyst is coated on a flow-through monolith substrate (i.e. a honeycomb monolithic catalyst support structure with many small, parallel channels running axially through the entire part) or filter monolith substrate such as a wall-flow filter etc. The molecular sieve catalyst for use in the present invention can be coated, e.g. as a washcoat component, on a suitable monolith substrate, such as a metal or ceramic flow through monolith substrate or a filtering substrate, such as a wall-flow filter or sintered metal or partial filter (such as is disclosed in WO 01/80978 or EP 1057519, the latter document describing a substrate comprising convoluted flow paths that at least slows the passage of soot -24 -therethrough). Alternatively, the molecular sieves for use in the present invention can be synthesized directly onto the substrate. Alternatively, the molecular sieve catalysts according to the invention can be formed into an extruded-type flow through catalyst.
Washcoat compositions containing the molecular sieves for use in the present invention for coating onto the monolith substrate for manufacturing extruded type substrate monoliths can comprise a binder selected from the group consisting of alumina, silica, (non molecular sieve) silica-alumina, naturally occurring clays, Ti02, Zr02, and Sn07.
In one embodiment, the at least one reactant, e.g., nitrogen oxides, are reduced with the reducing agent at a temperature of at least 100°C. In another embodiment, the at least one io reactant are reduced with the reducing agent at a temperature from about 150°C to 750°C. In a particular embodiment, the temperature range is from 175 to 550°C, or more particularly from to 400°C.
For a reactant including nitrogen oxides, the reduction of nitrogen oxides may be carried out in the presence of oxygen or in the absence of oxygen. The source of nitrogenous reductant is can be ammonia per se, hydrazine or any suitable ammonia precursor (such as urea ((NH2)2C0)), ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate or ammonium formate.
The method may be performed on a gas derived from a combustion process, such as from an internal combustion engine (whether mobile or stationary), a gas turbine and coal or oil fired power plants. The method may also be used to treat gas from industrial processes such as refining, from refinery heaters and boilers, furnaces, the chemical processing industry, coke ovens, municipal waste plants and incinerators, coffee roasting plants, etc. In a particular embodiment, the method is used for treating exhaust gas from a vehicular intemal combustion engine with a lean!rich cycle, such as a diesel engine, a gasoline engine, or an engine powered by liquid petroleum gas or natural gas.
For a reactant including nitrogen oxides, the nitrogenous reductant may be metered into the flowing exhaust gas only when it is determined that the molecular sieves catalyst is capable of catalyzing NO reduction at or above a desired efficiency, such as at above 100°C, above 150°C or above 175°C. The determination by the control means can be assisted by one or more suitable sensor inputs indicative of a condition of the engine selected from the group consisting of: exhaust gas temperature, catalyst bed temperature, accelerator position, mass flow of exhaust gas in the system, manifold vacuum, ignition timing, engine speed, lambda value of the -25 -exhaust gas, the quantity of fitel injected in the engine, the position of the exhaust gas recireulation (EGR) valve and thereby the amount of EGR and boost pressure.
Metering may be controlled in response to thc quantity of nitrogen oxides in the exhaust gas determined either directly (using a suitable NOx sensor) or indirectly, such as using pre-correlated look-up tables or maps -stored in the control means -correlating any one or more of the abovementioned inputs indicative of a condition of the engine with predicted NOx content of the exhaust gas.
The invention can also be defined according to any one of the following definitions: According to a first aspect, a method for using a catalyst comprising exposing a catalyst io to at least one reactant in a chemical process, wherein the catalyst comprises copper and a small pore molecular sieve, the chemical process undergoes at least one period of exposure to a reducing atmosphere, the catalyst has an initial activity before exposure to the reducing atmosphere and a final activity after the at least one period of exposure to the reducing atmosphere, wherein the final activity is within 30% of the initial activity at atemperaturebetween 150 and 650°C.
* According to a second aspect, a method for using a catalyst comprising: exposing a catalyst comprising copper and a small-pore molecular sieve to a reducing atmosphere, and contacting the catalyst with at least one reactant in a non-reducing atmosphere, wherein said contacting occurs subsequent to said exposing, wherein the catalyst has an initial activity before exposure to the reducing atmosphere and a final activity after the at least one period of exposure to the reducing atmosphere, wherein the final activity is within 30% of the initial activity at a temperature between 150 and 650°C.
* Amcthodaccordingtothefirstaspect,whereinthecatalysthasaflnalactivitythatis within 5% of the initial activity at a temperature between 200 and 500°C.
25. A method according to the first aspect, wherein the catalyst has a final activity that is within 3% of the initial activity at a temperature between 250 and 350t * A method according to the first aspect, wherein the at least one reactant comprises nitrogen oxides and a selective catalytic reduetant, wherein optionally the selective catalytic reductant comprises ammonia and where the reductant comprises ammonia, optionally the at least one reactant further comprises oxygen.
-26 - * A method according to the first aspect, wherein the small pore molecular sieve is selected from the group consisting of aluminosilicate molecular sieves, metal-substituted aluminosilicate molecular sieves, and aluminophosphate molecular sieves.
* A method according to the first aspect, wherein the small pore molecular sieves is selected from the group of Framework Type Codes consisting of: ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB, EDI, EPI, Em, GIS, GOO, IHW, ITE, ITW, LEY, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAy, Sly, THO, TSC, IJEI, UN, VNI, YIJG and ZON.
* A method according to the first aspect, wherein the small pore molecular sieves containing a maximum ring size of eight tetrahedral atoms is selected from the group of Framework Type Codes consisting of CHA, LEY, ERI and DDR.
* A method according to the first aspect, wherein the small pore molecular sieve comprises a CHA Framework Type Code SAPO-34.
* A method according to the first aspect, wherein the small pore molecular sieve is Is selected from the group consisting of a CHA Framework Type Code SSZ-13, a LEY Framework Type Code Nu-3, an AEI Framework Type Code SAPO-iS, an ERI Framework Type Code ZSM-34, a DDR Framework Type Code sigma-I, and mixtures thereof * A method according to the first aspect, wherein the at least one period of exposure to a reducing atmosphere is repeated exposure to a high temperature reducing atmosphere, optionally wherein the high temperature reducing atmosphere occurs at a temperature from about 150°C to 850°C.
* A method according to the first aspect, wherein the at least one period of exposure to a reducing atmosphere occurs during a lean/rich aging cycle in an exhaust gas treatment system, optionally wherein the lean/rich aging cycle occurs repeatedly.
* A method according to the first aspect, wherein the chemical process is selective catalytic reduction of NOx in an internal combustion engine exhaust gas.
* A method according to the first aspect, wherein the chemical process is catalyzed soot filter regeneration.
* A method according to the first aspect, wherein the chemical process is lean NO trap and selective catalytic reduction.
-27 -According to a third aspect, a method of using a catalyst comprising exposing a catalyst to at least one reactant comprising nitrogen oxides in a chemical process comprising exhaust gas treatment, wherein the catalyst comprises copper and a small pore molecular sieve framework having a maximum ring size of eight tetrahedral atoms selected from the group of Framework Type Codes consisting of Cl-IA, LEV, FRI and DDR, the chemical process undergoes at least one period of exposure to a reducing atmosphere, the catalyst has an initial activity, and the catalyst has a final activity after the at least one period of exposure to the reducing atmosphere, wherein the final activity is within 10% of the initial activity at a tcmperaturc between 250 and 350°C.
10. A method according to the third aspect, wherein the catalyst has a final activity that is within 3% of the initial activity at a temperature between 250 and 350°C.
* A method according to the first aspect, wherein the activity is NO conversion.
The entire contents of any and all patents and references cited herein are incorporated is herein by reference.
EXAMPLES
Ahhough the invention is illustrated and described herein with reference to specific embodiments, the invention is not intended to be limited to the details shown. Rather, various modifications may bc madc in the details within the scope and range of equivalents of the claims and without departing from the invention.
1. Steady State SCR Evaluation Steady-state selective catalytic reduction (SCR) activity tests were conducted in a quartz reactor of 24 inches in length, and uniformly heated by two tube ifimace units of 12 inches length. Experiments were performed at a gas hourly space velocity of 30,000 hf' utilizing catalyst dimensions of 1 inch diameter x 1 inch length. All gas lines directly connected to the reactor were maintained at 130 °C by heating tape to prevent gas species adsorption on the walls of the gas line. Water vapor was provided by a water bomb, which was constantly maintained at 70°C.
Prior to reaching the catalyst bed, the feed gas was heated and mixed upstream in the reactor via an inert thermal mass. The temperature of the gas stream was monitored at the catalyst inlet, center of the catalyst bed, and at the outlet by k-type thermocouples. Reacted feed gas was analyzed by a FTIR downstream from the catalyst bed at a sampling rate of 1.25 s -28 -The composition of the inlet feed gas could be determined by sampling from a bypass valve located upstream of the reactor.
Steady-state 5CR experiments were initially performed on catalyst samples that had been hydrothermally (HT) aged at 700°C for 2 hours in the presence of air containing 4.5% H20. All steady state experiments were conducted using a feed gas of NO and NH3 containing 350 ppm of NO, with an ammonia-to-NO (ANR) ratio of 1 (i.e., 350 ppm of NH5). The remainder of the feed gas composition was as follows: 14% 02, 4.6% H20, 5% C02, balance N2. The steady-state NO conversion was determined at catalyst bed temperatures of 150°C, 200°C, 250°C, 350°C, 450°C, 550°C, and 650°C.
io Catalysts were then aged under lean-rich cycling conditions at 600°C for 12 h. The lean portion of the cycle consisted of exposure to 200 ppm NO, 10% 02,5% H20, 5% CO2 inN2 for S seconds at a space velocity of 30,000 h1. The rich portion of the cycle consisted of exposure to200ppmNO, S000ppmC3H6, l.3%H2,4%C0, 1%02, 5%H50, 5%CO2inN2for 15 seconds. After the aging, steady-state SCR experiments were performed as described above.
is In Figure 3, the NO conversion efficiency is shown for embodiments of the present invention and a comparative example. Cu/SAPO-34, Cu/Nu-3 and Cu/SSZ-13, small pore molecular sieve catalysts according to embodiments of the invention, are shown after having undergone the above described hydrothermal aging treatment and lean/rich aging treatment, respectively. A comparative example showing Cu/Beta, a large pore molecular sieve catalyst, is also shown after both hydrothermal aging and lean/rich aging. As is evident, the small pore molecular sieve catalysts demonstrated enhanced NOx conversion efficiencies especially in the temperature window of 200 to 500CC.
2. NAC+S(:R Experiments NOx adsorber catalyst (NAC) and SCR cores were initially hydrothermally aged at 750°C for 16 hours in a 4.5% 1-120 in air gas mixture. Samples were then mounted in the same reactor setup described above with the NAC catalyst mounted directly in front of the SCR catalyst. The catalysts were aged at 600°C for 12 hours under the lean-rich aging conditions described above (5 seconds lean/IS seconds rich).
The catalysts were then cooled to 450°C under lean-rich cycling (60 seconds lean/S seconds rich, same gas compositions). At 450°C, 25 lean-rich cycles were completed (60 seconds lean/S seconds rich) with the last five cycles used to determine an average cycle NOx conversion for the catalyst. After the 25th cycle, the catalyst was held under the lean gas -29 -composition for 5 minutes. The catalyst was then cooled and evaluated at 400°C, 350°C, 300°C, 250°C, 200°C, and 175°C following the aforementioned cycle procedure.
In Figure 4, the NOx conversion efficiency is shown for embodiments of the present invention and two comparative examples. NAC+Cu/SAPO-34 and NAC+ Cu!SSZ-13, small pore molecular sieve catalysts according to embodiments of the invention are shown after having undergone the above described leanirich aging treatment. A comparative example showing NAC alone and NAC+Fe/Beta, a large pore molecular sieve catalyst, is also shown after lean/rich aging. As is evident, the small pore molecular sieve catalysts demonstrate enhanccd NOx convcrsion efficiencies comparable to and/or bettcr than NAC alone or NAC-f-Fe/Beta, especially in the temperature window of 250 to 450°C.
While preferred embodiments of the invention have been shown and described herein, it will be understood that such embodiments are provided by way of example only. Numerous variations, changes and substitutions will occur to those skilled in the art without departing from the spirit of the invention. Accordingly, it is intended that the appended claims cover all such is variations as fall within the spirit and scope of the invention.
Claims (11)
- -30 -CLAIMS: A system for treating exhaust gas from a yehicular lean-burn internal combustion engine with a leanirich cycle, which system comprising a NO adsorber catalyst and a downstream NH3-selectiye catalytic reduction (SCR) catalyst, wherein the NH3-SCR catalyst comprises copper supported on a molecular sieve, wherein the molecular sieve (a) has a maximum ring size of eight tetrahedral atoms; (b) is selected from the group consisting of aluminosilicate molecular sieves, metal-substituted aluminosilicate molecular sieves, and aluminophosphate molecular sieves; and (c) has a Framework Type Code selected from the group consisting of AET, LEY, EM and DDR.
- 2. The system according to claim 1, wherein the molecular sieve has a silica-to-alumina ratio of 8 to 150.
- 3. The system according to claim I or 2, wherein the total copper in the molecular sieve is is from 0.5 to 5 weight pcrccnt.
- 4. The system of according to claim 1,2 or 3, wherein the NO,. adsorber catalyst comprises a precious metal and a basic material selected from the group consisting of an ailcali metal, an alkaline earth metal, and a rare earth metal.
- 5. The system according to any preceding claim, wherein the NH3-SCR catalyst is coated on a substratc monolith.
- 6. The system according to any of claims I to 4, wherein the NT-13-SCR catalyst is formed as an extruded-type catalyst.
- 7. The system according to any of claims 5, wherein thc substrate monolith is a filter monolith substrate.
- 8. The system according to any preceding claim, wherein the AEI Framework Type Code molecular sieve is AIPO-18, SAPO-18, SIZ-8 or SSZ-39.
- 9. A vehicular diesel engine, gasoline engine, or an engine powered by liquid petroleum gas or ilatural gas comprising an exhaust systcm according to any prcccding claim. -31 -
- 10. A method for using a NW-selective catalytic reduction (SCR) catalyst for treating NO in an exhaust gas of a vehicular lean-burn internal combustion engine with a lean/rich cycle, which method comprising: (i) generating and releasing NH3 on a NO adsorber catalyst and storing released NH3 on a NH3-SCR catalyst downsfream of the NO,. adsorber catalyst during a rich phase of the cycle; and (ii) reducing NO,. that slips through the NO,. adsorber catalyst on the NH3-SCR catalyst with NH3 in a lean phase of the cycle, wherein the NH3-SCR catalyst comprises copper supported on a molecular sieve, wherein the molecular sieve (a) has a maximum ring size of eight tetrahedral atoms; (b) is selected from the Ct) group consisting of aluminosilicatc molecular sieves, metal-substituted aluminosilicatc molecular is sieves, and aluminophosphatc molecular sieves; and (c) has a Framework Type Code selected from the group consisting of AET, LEV, ERT and DDR. rIC)
- 11. The method according to claim 10, wherein the rich phase of the cycle is generated during one or more events selected from regeneration of a catalysed soot filter, regeneration of the NO,. adsorber catalyst and NO,. adsorber catalyst desulfation.Amendments to the claims have been filed as follows: CLAIMS: 1. A system for treating exhaust gas from a vehicular lean-bum intemal combustion engine with a lean/rich cycle, which system comprising a NO,. adsorber catalyst and a downstream NH3-selective catalytic reduction (SCR) catalyst, wherein the NH3-SCR catalyst comprises copper supported on a molecular sieve, wherein the molecular sieve (a) has a maximum ring size of eight tetrahedral atoms; (b) is selected from the group consisting of aluminosilicate molecular sieves, metal-substituted aluniinosilicate molecular sieves, and aluminophosphate molecular sieves; and (c) has a Framework Type Code selected from the group consisting of LEV, ERI and DDR.2. A system according to claim, wherein the aluminophosphate molecular sieve is an aluminophosphate (AIPO) molecular sieve, a metal substituted (MeAIPO) molecular sieve, a silico-aluminophosphate (SAPO) molecular sieve or a metal substituted silico-aluminophosphate (MeAPSO) molecular sieve. I53. The system according to claim 1, wherein the molecular sieve is an aluminosilicate molecular sieve and has a silica-to-alumina ratio of 8 to ISO.4. The system according to claim 1, 2 or 3, wherein the total copper in the molecular sieve is from 0.5 to 5 weight percent.5. The system of according to claim 1, 2, 3 or 4, wherein the NO,. adsorber catalyst comprises a precious metal and a basic material selected from the group consisting of an alkali metal, an alkaline earth metal, and a rare earth metal.6, The system according to any preceding claim, wherein the N1-13-SCR catalyst is coated on a substrate monolith.7. The system according to any of claims 1 to 5, wherein the NH3-SCR catalyst is formed as an extruded-type catalyst.8. The system according to claim 6, wherein the substrate monolith is a filter monolith substrate, s 9. A vehicular diesel engine, gasoline engine, or an engine powered by liquid petroleum gas or natural gas comprising an exhaust system according to any preceding claim.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1402348.5A GB2507902B (en) | 2009-04-17 | 2010-04-19 | Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17035809P | 2009-04-17 | 2009-04-17 | |
US31283210P | 2010-03-11 | 2010-03-11 | |
GB1119664.9A GB2482094B (en) | 2009-04-17 | 2010-04-19 | Small pore molecular sieve supported copper catalysts durable against lean/rich ageing for the reduction of nitrogen oxides |
PCT/US2010/031617 WO2010121257A1 (en) | 2009-04-17 | 2010-04-19 | Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides |
Publications (3)
Publication Number | Publication Date |
---|---|
GB201320065D0 GB201320065D0 (en) | 2013-12-25 |
GB2507006A true GB2507006A (en) | 2014-04-16 |
GB2507006B GB2507006B (en) | 2014-11-19 |
Family
ID=42313699
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB1119664.9A Active GB2482094B (en) | 2009-04-17 | 2010-04-19 | Small pore molecular sieve supported copper catalysts durable against lean/rich ageing for the reduction of nitrogen oxides |
GB1402348.5A Active GB2507902B (en) | 2009-04-17 | 2010-04-19 | Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides |
GB1320065.4A Active GB2507006B (en) | 2009-04-17 | 2010-04-19 | Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB1119664.9A Active GB2482094B (en) | 2009-04-17 | 2010-04-19 | Small pore molecular sieve supported copper catalysts durable against lean/rich ageing for the reduction of nitrogen oxides |
GB1402348.5A Active GB2507902B (en) | 2009-04-17 | 2010-04-19 | Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides |
Country Status (10)
Country | Link |
---|---|
US (8) | US7998443B2 (en) |
EP (2) | EP2419209A1 (en) |
JP (4) | JP5767206B2 (en) |
KR (3) | KR102180723B1 (en) |
CN (2) | CN102802791A (en) |
BR (1) | BRPI1015166A2 (en) |
DK (1) | DK2995367T3 (en) |
GB (3) | GB2482094B (en) |
RU (1) | RU2546666C2 (en) |
WO (1) | WO2010121257A1 (en) |
Families Citing this family (91)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7998423B2 (en) * | 2007-02-27 | 2011-08-16 | Basf Corporation | SCR on low thermal mass filter substrates |
JP5777339B2 (en) | 2007-04-26 | 2015-09-09 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Publiclimited Company | Transition metal / zeolite SCR catalyst |
US8512657B2 (en) * | 2009-02-26 | 2013-08-20 | Johnson Matthey Public Limited Company | Method and system using a filter for treating exhaust gas having particulate matter |
US9662611B2 (en) | 2009-04-03 | 2017-05-30 | Basf Corporation | Emissions treatment system with ammonia-generating and SCR catalysts |
DE102010027883A1 (en) | 2009-04-17 | 2011-03-31 | Johnson Matthey Public Ltd., Co. | Process for using a catalyst with copper and a small pore molecular sieve in a chemical process |
WO2010121257A1 (en) * | 2009-04-17 | 2010-10-21 | Johnson Matthey Public Limited Company | Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides |
EP2521615A1 (en) * | 2009-10-14 | 2012-11-14 | Basf Se | Copper containing levyne molecular sieve for selective reduction of nox |
HUE027305T2 (en) | 2010-02-01 | 2016-10-28 | Johnson Matthey Plc | Oxidation catalyst |
EP2555853A4 (en) * | 2010-03-11 | 2014-04-16 | Johnson Matthey Plc | DISORDERED MOLECULAR SIEVE SUPPORTS FOR THE SELECTIVE CATALYTIC REDUCTION OF NOx |
US8987162B2 (en) | 2010-08-13 | 2015-03-24 | Ut-Battelle, Llc | Hydrothermally stable, low-temperature NOx reduction NH3-SCR catalyst |
US8987161B2 (en) | 2010-08-13 | 2015-03-24 | Ut-Battelle, Llc | Zeolite-based SCR catalysts and their use in diesel engine emission treatment |
EP2465606A1 (en) * | 2010-12-16 | 2012-06-20 | Umicore Ag & Co. Kg | Zeolith-based catalytic converter with improved catalytic activity for reducing nitrogen oxides |
US20120134916A1 (en) * | 2011-02-28 | 2012-05-31 | Fedeyko Joseph M | High-temperature scr catalyst |
US8101146B2 (en) | 2011-04-08 | 2012-01-24 | Johnson Matthey Public Limited Company | Catalysts for the reduction of ammonia emission from rich-burn exhaust |
JP5767024B2 (en) * | 2011-06-01 | 2015-08-19 | トヨタ自動車株式会社 | Exhaust gas purification device for internal combustion engine |
RU2634702C2 (en) * | 2011-07-27 | 2017-11-03 | Джонсон Мэтти Паблик Лимитед Компани | Low-phosphorus chabazites |
US9138731B2 (en) | 2011-08-03 | 2015-09-22 | Johnson Matthey Public Limited Company | Extruded honeycomb catalyst |
US9981256B2 (en) | 2011-12-02 | 2018-05-29 | Pq Corporation | Stabilized microporous crystalline material, the method of making the same, and the use for selective catalytic reduction of NOx |
BR112014012846B1 (en) * | 2011-12-02 | 2021-10-26 | Pq Corporation | CRYSTALLINE ALUMINOSILICATE MATERIAL, THE METHOD OF MANUFACTURING IT, AND SELECTIVE CATALYTIC REDUCTION METHOD OF NITROGEN OXIDES IN EXHAUST GAS |
CN104520548B (en) * | 2012-04-27 | 2018-09-07 | 优美科两合公司 | Method and system for purifying the exhaust gas from internal combustion engine |
JP5983290B2 (en) * | 2012-10-18 | 2016-08-31 | 東ソー株式会社 | Silicoaluminophosphate and nitrogen oxide reduction catalyst using the same |
WO2014038636A1 (en) * | 2012-09-07 | 2014-03-13 | 東ソー株式会社 | Silicoaluminophosphate salt and nitrogen oxide reduction catalyst using same |
CA2888517C (en) | 2012-10-19 | 2020-10-06 | Basf Corporation | 8-ring small pore molecular sieve as high temperature scr catalyst |
CN104736241B (en) | 2012-10-19 | 2020-05-19 | 巴斯夫公司 | 8-ring small pore molecular sieve with promoter to improve low temperature performance |
JP6070230B2 (en) * | 2013-02-01 | 2017-02-01 | 東ソー株式会社 | AFX type silicoaluminophosphate, method for producing the same, and nitrogen oxide reduction method using the same |
JP6070229B2 (en) * | 2013-02-01 | 2017-02-01 | 東ソー株式会社 | SAV type silicoaluminophosphate, method for producing the same, and nitrogen oxide reduction method using the same |
CN103127951B (en) * | 2013-03-05 | 2015-02-04 | 四川中自尾气净化有限公司 | Low temperature SCR catalyst used for diesel car tail gas denitration and preparation method |
US9802182B2 (en) | 2013-03-13 | 2017-10-31 | Basf Corporation | Stabilized metal-exchanged SAPO material |
US9044744B2 (en) * | 2013-03-15 | 2015-06-02 | Johnson Matthey Public Limited Company | Catalyst for treating exhaust gas |
US9114363B2 (en) | 2013-03-15 | 2015-08-25 | General Electric Company | Aftertreatment system for simultaneous emissions control in stationary rich burn engines |
BR112015029664A2 (en) * | 2013-05-31 | 2017-07-25 | Johnson Matthey Plc | diesel particulate filter, system for treating a poor burning exhaust gas, and method for reducing soot in a poor burning exhaust gas |
BR112015029656A2 (en) * | 2013-05-31 | 2017-07-25 | Johnson Matthey Plc | diesel particulate filter, system for treating a poor burning exhaust gas, and method for reducing soot in a poor burning exhaust gas |
DE102014112413A1 (en) * | 2013-08-30 | 2015-03-05 | Johnson Matthey Public Limited Company | ZEOLITE MIXING CATALYSTS FOR THE TREATMENT OF EXHAUST GAS |
US9782761B2 (en) | 2013-10-03 | 2017-10-10 | Ford Global Technologies, Llc | Selective catalytic reduction catalyst |
US9700862B2 (en) | 2013-10-16 | 2017-07-11 | X-Pert Paint Mixing Systems, Inc. | Storage, mixing, dispensing and tracking system |
RU2744763C2 (en) | 2013-12-02 | 2021-03-15 | Джонсон Мэтти Паблик Лимитед Компани | Synthesis of zeolite aei |
JP2017501329A (en) * | 2013-12-06 | 2017-01-12 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Public Limited Company | Passive NOx adsorber containing precious metal and small pore molecular sieve |
GB2522435B (en) | 2014-01-23 | 2018-10-03 | Johnson Matthey Plc | Catalytic extruded solid honeycomb body |
US20150231617A1 (en) * | 2014-02-19 | 2015-08-20 | Ford Global Technologies, Llc | Fe-SAPO-34 CATALYST FOR USE IN NOX REDUCTION AND METHOD OF MAKING |
WO2015125496A1 (en) * | 2014-02-21 | 2015-08-27 | Toyota Jidosha Kabushiki Kaisha | SELECTIVE NOx REDUCTION CATALYST |
DE102014205783A1 (en) * | 2014-03-27 | 2015-10-01 | Johnson Matthey Public Limited Company | Catalyst and method for producing a catalyst |
RU2672095C2 (en) | 2014-04-07 | 2018-11-12 | Хальдор Топсеэ А/С | Method for producing metal exchanged metallo-aluminophosphates by solid-state ion exchange at low temperatures |
WO2015154829A1 (en) | 2014-04-07 | 2015-10-15 | Haldor Topsøe A/S | Method for producing metal exchanged microporous materials by solid-state ion exchange |
US20150290632A1 (en) * | 2014-04-09 | 2015-10-15 | Ford Global Technologies, Llc | IRON AND COPPER-CONTAINING CHABAZITE ZEOLITE CATALYST FOR USE IN NOx REDUCTION |
CN103920392B (en) * | 2014-04-17 | 2016-08-17 | 山东大学 | A kind of technique utilizing lean oxygen-enriched alternation response to carry out denitrating flue gas |
CN105085315B (en) * | 2014-05-04 | 2017-02-22 | 中国科学院大连化学物理研究所 | Method for preparing nitrile compounds by catalytic oxidation of amine |
GB2530129B (en) * | 2014-05-16 | 2016-10-26 | Johnson Matthey Plc | Catalytic article for treating exhaust gas |
US10850265B2 (en) * | 2014-06-18 | 2020-12-01 | Basf Corporation | Molecular sieve catalyst compositions, catalytic composites, systems, and methods |
CN106795817B (en) | 2014-10-16 | 2020-04-07 | 康明斯排放处理公司 | Aftertreatment system for dual fuel engine |
RU2710595C2 (en) * | 2014-10-30 | 2019-12-30 | Басф Корпорейшн | Mixed catalytic compositions of metal coarse-crystalline molecular sieves, catalytic products, systems and methods |
GB2538877B (en) * | 2014-12-08 | 2017-04-26 | Johnson Matthey Plc | Passive NOx adsorber |
JP6292159B2 (en) * | 2015-04-13 | 2018-03-14 | トヨタ自動車株式会社 | Exhaust gas purification catalyst |
MX2017016112A (en) * | 2015-06-12 | 2018-02-21 | Basf Corp | Exhaust gas treatment system. |
EP3310477A1 (en) * | 2015-06-18 | 2018-04-25 | Johnson Matthey Public Limited Company | Single or dual layer ammonia slip catalyst |
ITUB20154976A1 (en) * | 2015-10-16 | 2017-04-16 | Lavazza Luigi Spa | Process for the treatment of gaseous effluents developed in a coffee roasting plant. |
CN106622356B (en) * | 2015-11-03 | 2019-03-05 | 中触媒新材料股份有限公司 | A kind of copper modified molecular screen selective reduction catalyst and its preparation method and application |
CN106824261B (en) * | 2015-12-03 | 2019-10-11 | 中国石油化工股份有限公司 | Ni-SSZ-13 catalyst, preparation method and its usage |
CN107233932A (en) * | 2016-03-29 | 2017-10-10 | 巴斯夫公司 | Sulfur method for SCR catalyst |
GB2551871A (en) * | 2016-04-22 | 2018-01-03 | Johnson Matthey Plc | STA-18, A new member of the SFW family of molecular sieve zeotypes, methods of preparation and use |
JP6975728B2 (en) | 2016-06-08 | 2021-12-01 | ビーエーエスエフ コーポレーション | Copper-promoted gumerin zeolite and its use in selective catalytic reduction of NOx |
WO2018025244A1 (en) * | 2016-08-05 | 2018-02-08 | Basf Corporation | Selective catalytic reduction articles and systems |
JP7233364B2 (en) * | 2016-10-18 | 2023-03-06 | ビーエーエスエフ コーポレーション | Low temperature NOx reduction using H2-SCR for diesel vehicles |
BR112019008207A2 (en) | 2016-10-24 | 2019-07-09 | Basf Corp | exhaust gas treatment systems, method for treating an exhaust stream and catalytic article |
GB2556453A (en) | 2016-10-26 | 2018-05-30 | Johnson Matthey Plc | Hydrocarbon injection through small pore CU-zeolite catalyst |
EP3323785A1 (en) * | 2016-11-18 | 2018-05-23 | Umicore AG & Co. KG | Crystalline zeolites with eri/cha intergrowth framework type |
JP2020514042A (en) * | 2017-03-20 | 2020-05-21 | ビーエーエスエフ コーポレーション | Selective catalytic reduction articles and systems |
CN106925266A (en) * | 2017-03-22 | 2017-07-07 | 无锡威孚环保催化剂有限公司 | Single coating three-way catalyst |
JP7254712B2 (en) * | 2017-04-04 | 2023-04-10 | ビーエーエスエフ コーポレーション | On-board ammonia and hydrogen generation |
WO2018224651A2 (en) | 2017-06-09 | 2018-12-13 | Basf Se | Catalytic article and exhaust gas treatment systems |
KR20230123521A (en) | 2017-06-09 | 2023-08-23 | 바스프 코포레이션 | Catalytic article and exhaust gas treatment systems |
CN109250728B (en) * | 2017-07-12 | 2022-02-18 | 中国科学院大连化学物理研究所 | Cu-SAPO molecular sieve synthesis method, synthesized Cu-SAPO molecular sieve and application |
KR20200055744A (en) | 2017-10-12 | 2020-05-21 | 바스프 코포레이션 | Combined NOx absorber and SCR catalyst |
CN109701618B (en) * | 2017-10-26 | 2021-08-03 | 中国石油化工股份有限公司 | AEI composite molecular sieve and synthesis method thereof |
CN109701621B (en) * | 2017-10-26 | 2021-10-01 | 中国石油化工股份有限公司 | SSZ-13/SSZ-39 composite structure molecular sieve catalyst, preparation method and application thereof |
EP3707356A4 (en) | 2017-11-10 | 2021-05-12 | BASF Corporation | Catalyzed soot filter with reduced ammonia oxidation |
CN108636431A (en) * | 2018-04-20 | 2018-10-12 | 中自环保科技股份有限公司 | A kind of wall-flow type LNT catalyst, preparation method and application |
CN108906117A (en) * | 2018-07-06 | 2018-11-30 | 郑州三希新材料科技有限公司 | A kind of material for air purification of novel visible color change and preparation method thereof |
CN109603811B (en) * | 2018-12-28 | 2021-07-06 | 大唐南京环保科技有限责任公司 | Preparation method of flat plate type denitration catalyst |
CN109590016B (en) * | 2018-12-31 | 2021-10-29 | 天津大学 | Catalyst for diesel engine based on modified hydrotalcite derived oxide and preparation method thereof |
CN109675615A (en) * | 2019-01-09 | 2019-04-26 | 无锡威孚环保催化剂有限公司 | Improve low temperature NOxThe lean-burn NO of transformation efficiencyxTrap catalyst and preparation method thereof |
CN110252392A (en) * | 2019-07-18 | 2019-09-20 | 付华 | A kind of cerium modified Cu-SAPO-34 molecular sieve catalyst and preparation method thereof |
CN110479091A (en) * | 2019-08-23 | 2019-11-22 | 山东瀚江环保科技有限公司 | A kind of ceramic filter material and preparation method thereof |
CN110876957B (en) * | 2019-10-31 | 2021-01-22 | 山东国瓷功能材料股份有限公司 | Molecular sieve Cu-SSZ-13, synthesis method, catalyst and application thereof |
CN110642365B (en) * | 2019-11-11 | 2021-10-12 | 浙江晶立捷环境科技有限公司 | Method for advanced treatment of wastewater by subcritical oxidation technology |
CN111762795B (en) * | 2020-07-13 | 2022-10-14 | 包头稀土研究院 | Molecular sieve containing rare earth elements and production method thereof |
CN111762794B (en) * | 2020-07-13 | 2022-08-05 | 包头稀土研究院 | Molecular sieve and preparation method thereof |
CN112547099B (en) * | 2020-12-23 | 2023-03-21 | 天津水泥工业设计研究院有限公司 | Low-temperature cerium-based sulfur-resistant water-resistant denitration catalyst and preparation method thereof |
CN115055206A (en) * | 2021-08-27 | 2022-09-16 | 华中科技大学 | Acidic site protection modified Cu-SAPO-34 catalyst and preparation method and application thereof |
CN113976172A (en) * | 2021-10-12 | 2022-01-28 | 中山大学 | Preparation and application of assistant doped Cu-SSZ-39 catalyst with high hydrothermal stability |
CN114588933A (en) * | 2022-02-08 | 2022-06-07 | 凯龙蓝烽新材料科技有限公司 | Preparation method and application of ABC-6 small-pore molecular sieve SCR catalyst |
CN115739172A (en) * | 2022-12-02 | 2023-03-07 | 润和科华催化剂(上海)有限公司 | Remove N in coordination 2 Catalyst for O and NO and preparation method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2414081A2 (en) * | 2009-04-03 | 2012-02-08 | BASF Corporation | Emissions treatment system with ammonia-generating and scr catalysts |
Family Cites Families (40)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10020170C1 (en) * | 2000-04-25 | 2001-09-06 | Emitec Emissionstechnologie | Process for removing soot particles from the exhaust gas of internal combustion engine comprises feeding gas through collecting element, and holding and/or fluidizing until there is sufficient reaction with nitrogen dioxide in exhaust gas |
US4735930A (en) * | 1986-02-18 | 1988-04-05 | Norton Company | Catalyst for the reduction of oxides of nitrogen |
WO1993007363A1 (en) * | 1991-10-03 | 1993-04-15 | Toyota Jidosha Kabushiki Kaisha | Device for purifying exhaust of internal combustion engine |
JP3158444B2 (en) * | 1995-11-09 | 2001-04-23 | トヨタ自動車株式会社 | Method and apparatus for purifying exhaust gas of an internal combustion engine |
US5958818A (en) | 1997-04-14 | 1999-09-28 | Bulldog Technologies U.S.A., Inc. | Alkaline phosphate-activated clay/zeolite catalysts |
GB9808876D0 (en) * | 1998-04-28 | 1998-06-24 | Johnson Matthey Plc | Combatting air pollution |
US6182443B1 (en) | 1999-02-09 | 2001-02-06 | Ford Global Technologies, Inc. | Method for converting exhaust gases from a diesel engine using nitrogen oxide absorbent |
FI107828B (en) | 1999-05-18 | 2001-10-15 | Kemira Metalkat Oy | Systems for cleaning exhaust gases from diesel engines and method for cleaning exhaust gases from diesel engines |
DE19922961C2 (en) * | 1999-05-19 | 2003-07-17 | Daimler Chrysler Ag | Emission control system with internal ammonia production for nitrogen oxide reduction |
DE10001541B4 (en) * | 2000-01-14 | 2005-04-28 | Uhde Gmbh | Process for the removal of NOx and N¶2¶O from the residual gas of nitric acid production |
US6914026B2 (en) * | 2001-09-07 | 2005-07-05 | Engelhard Corporation | Hydrothermally stable metal promoted zeolite beta for NOx reduction |
US6912847B2 (en) * | 2001-12-21 | 2005-07-05 | Engelhard Corporation | Diesel engine system comprising a soot filter and low temperature NOx trap |
US6964157B2 (en) * | 2002-03-28 | 2005-11-15 | Ricardo, Inc | Exhaust emission control system and method for removal and storage of vehicle exhaust gas nitrogen oxides during cold operation |
US7332135B2 (en) * | 2002-10-22 | 2008-02-19 | Ford Global Technologies, Llc | Catalyst system for the reduction of NOx and NH3 emissions |
DE10300298A1 (en) * | 2003-01-02 | 2004-07-15 | Daimlerchrysler Ag | Exhaust gas aftertreatment device and method |
US7582202B2 (en) * | 2003-02-13 | 2009-09-01 | Akzo Nobel N.V. | Composition comprising a metal hydroxy salt, its preparation and use as catalyst or sorbent |
DE10308287B4 (en) * | 2003-02-26 | 2006-11-30 | Umicore Ag & Co. Kg | Process for exhaust gas purification |
JP2005111436A (en) * | 2003-10-10 | 2005-04-28 | Valtion Teknillinen Tutkimuskeskus | Method for catalytically eliminating nitrogen oxide and device therefor |
US7490464B2 (en) * | 2003-11-04 | 2009-02-17 | Basf Catalysts Llc | Emissions treatment system with NSR and SCR catalysts |
US7213395B2 (en) * | 2004-07-14 | 2007-05-08 | Eaton Corporation | Hybrid catalyst system for exhaust emissions reduction |
US7062904B1 (en) * | 2005-02-16 | 2006-06-20 | Eaton Corporation | Integrated NOx and PM reduction devices for the treatment of emissions from internal combustion engines |
US20070012032A1 (en) * | 2005-07-12 | 2007-01-18 | Eaton Corporation | Hybrid system comprising HC-SCR, NOx-trapping, and NH3-SCR for exhaust emission reduction |
US7472545B2 (en) * | 2006-05-25 | 2009-01-06 | Delphi Technologies, Inc. | Engine exhaust emission control system providing on-board ammonia generation |
US8580228B2 (en) * | 2006-12-27 | 2013-11-12 | Chevron U.S.A. Inc. | Treatment of cold start engine exhaust |
CN101668589B (en) * | 2007-02-27 | 2013-06-12 | 巴斯福催化剂公司 | Copper CHA zeolite catalysts |
US7998423B2 (en) * | 2007-02-27 | 2011-08-16 | Basf Corporation | SCR on low thermal mass filter substrates |
MY146586A (en) * | 2007-03-26 | 2012-08-30 | Pq Corp | Novel microporous crystalline material comprising a molecular sieve or zeolite having an 8-ring pore opening structure and methods of making and using same |
JP5777339B2 (en) * | 2007-04-26 | 2015-09-09 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Publiclimited Company | Transition metal / zeolite SCR catalyst |
CN101352681B (en) * | 2008-08-29 | 2010-12-22 | 浙江大学 | Low-temperature SCR catalyst using nitrogen-dopped activated carbon as carrier and preparation technique thereof |
EP2380663A4 (en) * | 2009-01-22 | 2017-05-10 | Mitsubishi Plastics, Inc. | Catalyst for removing nitrogen oxides and method for producing same |
WO2010108083A1 (en) * | 2009-03-20 | 2010-09-23 | Basf Catalysts Llc | EMISSIONS TREATMENT SYSTEM WITH LEAN NOx TRAP |
WO2010121257A1 (en) * | 2009-04-17 | 2010-10-21 | Johnson Matthey Public Limited Company | Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides |
KR20110024598A (en) * | 2009-09-02 | 2011-03-09 | 현대자동차주식회사 | Nox reduction device for diesel vehicles |
US8987162B2 (en) * | 2010-08-13 | 2015-03-24 | Ut-Battelle, Llc | Hydrothermally stable, low-temperature NOx reduction NH3-SCR catalyst |
US8701390B2 (en) * | 2010-11-23 | 2014-04-22 | International Engine Intellectual Property Company, Llc | Adaptive control strategy |
JP6450521B2 (en) * | 2010-12-02 | 2019-01-09 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーJohnson Matthey Public Limited Company | Metal-containing zeolite catalyst |
EP2463028A1 (en) * | 2010-12-11 | 2012-06-13 | Umicore Ag & Co. Kg | Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic removal of nitrogen oxides |
BR112014012846B1 (en) * | 2011-12-02 | 2021-10-26 | Pq Corporation | CRYSTALLINE ALUMINOSILICATE MATERIAL, THE METHOD OF MANUFACTURING IT, AND SELECTIVE CATALYTIC REDUCTION METHOD OF NITROGEN OXIDES IN EXHAUST GAS |
US9802182B2 (en) * | 2013-03-13 | 2017-10-31 | Basf Corporation | Stabilized metal-exchanged SAPO material |
DE102014117602A1 (en) * | 2014-09-12 | 2016-03-17 | Hyundai Motor Company | Catalyst system for internal combustion engine |
-
2010
- 2010-04-19 WO PCT/US2010/031617 patent/WO2010121257A1/en active Application Filing
- 2010-04-19 GB GB1119664.9A patent/GB2482094B/en active Active
- 2010-04-19 BR BRPI1015166A patent/BRPI1015166A2/en not_active Application Discontinuation
- 2010-04-19 JP JP2012505997A patent/JP5767206B2/en active Active
- 2010-04-19 EP EP10715069A patent/EP2419209A1/en not_active Ceased
- 2010-04-19 EP EP22186350.9A patent/EP4112168A1/en active Pending
- 2010-04-19 GB GB1402348.5A patent/GB2507902B/en active Active
- 2010-04-19 KR KR1020177035435A patent/KR102180723B1/en active IP Right Grant
- 2010-04-19 CN CN201080027683XA patent/CN102802791A/en active Pending
- 2010-04-19 RU RU2011146545/04A patent/RU2546666C2/en active
- 2010-04-19 DK DK15189846.7T patent/DK2995367T3/en active
- 2010-04-19 US US12/762,971 patent/US7998443B2/en active Active
- 2010-04-19 KR KR1020117026925A patent/KR101809040B1/en active IP Right Grant
- 2010-04-19 CN CN201610087631.0A patent/CN105749747A/en active Pending
- 2010-04-19 KR KR1020207000961A patent/KR20200007089A/en not_active Application Discontinuation
- 2010-04-19 GB GB1320065.4A patent/GB2507006B/en active Active
-
2011
- 2011-07-25 US US13/189,981 patent/US8101147B2/en active Active
- 2011-12-22 US US13/334,259 patent/US8182777B2/en active Active
-
2012
- 2012-05-02 US US13/462,379 patent/US8347614B2/en active Active
- 2012-12-04 US US13/693,408 patent/US8518355B2/en active Active
-
2013
- 2013-08-05 US US13/959,369 patent/US8753598B2/en active Active
-
2014
- 2014-04-25 US US14/262,052 patent/US9199195B2/en active Active
-
2015
- 2015-04-23 JP JP2015088421A patent/JP6363554B2/en active Active
- 2015-10-21 US US14/918,725 patent/US9802156B2/en active Active
-
2018
- 2018-06-27 JP JP2018121967A patent/JP6931628B2/en active Active
-
2020
- 2020-03-02 JP JP2020034602A patent/JP2020116573A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2414081A2 (en) * | 2009-04-03 | 2012-02-08 | BASF Corporation | Emissions treatment system with ammonia-generating and scr catalysts |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9802156B2 (en) | Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides | |
EP2995367B1 (en) | Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides | |
EP2150328B1 (en) | SCR METHOD AND SYSTEM USING Cu/SAPO-34 ZEOLITE CATALYST | |
WO2011112949A1 (en) | DISORDERED MOLECULAR SIEVE SUPPORTS FOR THE SELECTIVE CATALYTIC REDUCTION OF NOx | |
CN111468179A (en) | Catalyst for treating exhaust gas | |
US20230130212A1 (en) | Catalyst for treating exhaust gas | |
CN117813159A (en) | Catalyst for treating exhaust gas |