CN114247450B - Catalytic composition, catalyst layer, catalytic device and gas treatment system - Google Patents
Catalytic composition, catalyst layer, catalytic device and gas treatment system Download PDFInfo
- Publication number
- CN114247450B CN114247450B CN202111608402.6A CN202111608402A CN114247450B CN 114247450 B CN114247450 B CN 114247450B CN 202111608402 A CN202111608402 A CN 202111608402A CN 114247450 B CN114247450 B CN 114247450B
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- Prior art keywords
- catalyst
- ammonia slip
- catalytic
- catalyst layer
- layer
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- 239000003054 catalyst Substances 0.000 title claims abstract description 130
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims description 22
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 20
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- 238000011144 upstream manufacturing Methods 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical group 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910000421 cerium(III) oxide Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910000471 manganese heptoxide Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 47
- 239000002002 slurry Substances 0.000 description 38
- 239000007789 gas Substances 0.000 description 21
- 239000000843 powder Substances 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 9
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 229910002089 NOx Inorganic materials 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 229940071125 manganese acetate Drugs 0.000 description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 5
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 239000001272 nitrous oxide Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical compound O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- LSQZJLSUYDQPKJ-NJBDSQKTSA-N amoxicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=C(O)C=C1 LSQZJLSUYDQPKJ-NJBDSQKTSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- -1 fe 2O3 Chemical compound 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01D53/8631—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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8634—Ammonia
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
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- 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
- B01D53/9436—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/02—Preparation of nitrogen
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
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Abstract
The present invention relates to a catalytic composition, a catalyst layer, a catalytic device and a gas treatment system. The catalytic composition has improved ammonia oxidation catalytic activity.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a catalytic composition, a catalyst layer, a catalytic device and a gas treatment system.
Background
In an exhaust gas purification system for a diesel engine, nitrogen oxides (NO x) are subjected to Selective Catalytic Reduction (SCR) using ammonia (NH 3) as a reducing agent. In order to maximize NOx conversion, an excess of ammonia is typically employed. This results in the presence of excess NH 3 in the product after the SCR reaction.
The related art places an Ammonia slip catalyst (Ammonia SLIP CATALYST, ASC catalyst) downstream of a Selective Catalytic Reduction (SCR) catalyst to remove unreacted NH 3 that passes through the SCR catalyst. The ASC catalyst oxidizes NH 3 and produces N 2 and H 2 O as selectively as possible. The relevant reaction equations are shown below:
4NH3+3O2＝2N2+6H2O
2NH3+2O2＝N2O+3H2O
4NH3+5O2＝4NO+6H2O
4NH3+7O2＝4NO2+6H2O
the related art adopts a carrier such as titanium dioxide, aluminum oxide, silicon dioxide, zirconium oxide and the like to load noble metals (such as platinum, palladium or rhodium) as an ammonia slip catalyst.
Disclosure of Invention
The present disclosure provides a novel catalytic composition for use as an ammonia slip catalyst exhibiting significantly improved performance.
In some aspects, the present disclosure provides a catalytic composition comprising
(I) Tungsten oxide;
(ii) Zirconium oxide;
(iii) M oxide, M oxide including manganese oxide, cerium oxide, copper oxide, iron oxide, or a combination thereof.
In some embodiments, the molar ratio of the metal element in the tungsten oxide to the metal element in the zirconium oxide is 0.5 to 2.5 (e.g., 0.5 to 1,1 to 1.5, 1.5 to 2, 2 to 2.5, 0.8 to 1.2, 0.9 to 1.1, 1.8 to 2.2, or 1.9 to 2.1);
In some embodiments, the molar ratio of metal element in the tungsten oxide to total metal element in the M oxide is 0.5 to 2.5 (e.g., 0.5 to 1, 1 to 1.5, 1.5 to 2, 2 to 2.5, 0.8 to 1.2, 0.9 to 1.1, 1.8 to 2.2, or 1.9 to 2.1).
In some embodiments, the M oxide comprises a manganese oxide.
In some embodiments, the molar ratio of the metal element in the tungsten oxide to the metal element in the manganese oxide is 0.5 to 2.5 (e.g., 0.5 to 1,1 to 1.5, 1.5 to 2, 2 to 2.5, 0.8 to 1.2, 0.9 to 1.1, 1.8 to 2.2, or 1.9 to 2.1): 0.5 to 2.5 (e.g., 0.5 to 1,1 to 1.5, 1.5 to 2, 2 to 2.5, 0.8 to 1.2, 0.9 to 1.1, 1.8 to 2.2, or 1.9 to 2.1);
in some embodiments, the M oxide comprises a cerium oxide.
In some embodiments, the molar ratio of the metal element in the tungsten oxide to the total metal element in the cerium oxide is 0.5 to 2.5 (e.g., 0.5 to 1, 1 to 1.5, 1.5 to 2, 2 to 2.5, 0.8 to 1.2, 0.9 to 1.1, 1.8 to 2.2, or 1.9 to 2.1).
In some embodiments, the catalytic composition includes tungsten oxide, zirconium oxide, manganese oxide, and cerium oxide.
In some embodiments, the catalytic composition comprises tungsten oxide, zirconium oxide, manganese oxide, and cerium oxide, in the following proportions, in terms of the moles of the metal elements they each contain: tungsten element: zirconium element: manganese element: cerium element = 0.5-2.5 (e.g., 0.5-1, 1-1.5, 1.5-2, 2-2.5, 0.8-1.2, 0.9-1.1, 1.8-2.2, or 1.9-2.1): 0.5-2.5 (e.5-1, 1-1.5, 2.5-2, 2.8-2.2, 1.8-2.2, or 1.9-2.1.1).
In some embodiments, the catalytic composition comprises tungsten oxide, zirconium oxide, manganese oxide, and cerium oxide, in the following proportions, in terms of the moles of the metal elements they each contain: tungsten element: zirconium element: manganese element: cerium element=0.8 to 1.2 (e.g., 0.9 to 1.1), 0.8 to 1.2 (e.g., 0.9 to 1.1).
In some embodiments, the catalytic composition comprises tungsten oxide, zirconium oxide, manganese oxide, and cerium oxide, in the following proportions, in terms of the moles of the metal elements they each contain: tungsten element: zirconium element: manganese element: cerium element=1:1:1:1.
In some embodiments, the catalytic composition does not contain a platinum group metal element.
In some embodiments, the platinum group metal refers to platinum (Pt), palladium (Pd), osmium (Os), iridium (Ir), ruthenium (Ru), rhodium (Rh).
In some embodiments, the tungsten oxide is WO 3.
In some embodiments, the zirconium oxide is ZrO 2.
In some embodiments, the manganese oxide includes one or more of MnO, mnO 2、MnO3、Mn2O3、Mn2O5、Mn2O7, and Mn 3O4.
In some embodiments, the cerium oxide includes CeO 2、Ce2O3.
In some embodiments, the copper oxide includes one or more of Cu 2 O, cuO.
In some embodiments, the iron oxide comprises one or more of FeO, fe 2O3、Fe3O4.
In some embodiments, the catalytic composition is a powder.
In some embodiments, the D90 value of the powder of the catalytic composition is from 1 to 100 μm, such as from 1 to 50 μm, such as from 1 to 20 μm, such as from 1 to 10 μm.
In some aspects, the present disclosure provides for the use of the above-described catalytic composition as an ammonia slip catalyst.
In some embodiments, the ammonia slip catalyst described above is used to catalyze the oxidation of ammonia by oxygen to produce nitrogen and water.
In some embodiments, the ammonia slip catalyst described above is used to catalyze the following reactions:
4NH3+3O2＝2N2+6H2O。
in some aspects, the present disclosure provides a method of catalyzing the composition described above, comprising:
(1) Providing a solution containing metal ions (e.g., a salt solution of metal ions) in a corresponding proportion, according to the molar proportions of the respective metal elements in the catalytic composition;
(2) Adding alkali into the solution in the previous step to precipitate metal ions;
(3) Carrying out solid-liquid separation on the product of the last step, and collecting solids;
(4) Roasting the solid in the previous step;
Optionally, the method further comprises:
(5) Pulverizing the product of the last step.
In some embodiments, the solution of step (1) contains ammonium metatungstate (NH 4)6H2W12O40).
In some embodiments, the solution of step (1) contains manganese acetate Mn (CH 3COO)2).
In some embodiments, the solution of step (1) contains cerium nitrate Ce (NO 3)3).
In some embodiments, the solution of step (1) contains zirconyl nitrate ZrO (NO 3)2).
In some embodiments, the base in step (2) comprises aqueous ammonia at a concentration of 10 to 30wt% (e.g., 20 wt%).
In some embodiments, the solution is heated to 60-80 ℃ (e.g., 70 ℃) prior to the addition of the base in step (2).
In some embodiments, step (2) adds a base to the solution at a pH of 7.5 to 9 (e.g., 8).
In some embodiments, the solid-liquid separation in step (3) is filtration or centrifugation.
In some embodiments, step (3) further comprises the step of drying the collected solids at 100 to 150 ℃ (e.g., 120 ℃).
In some embodiments, the firing in step (4) is performed at 700 to 1000 ℃ (e.g., 800 to 900 ℃).
In some embodiments, the time of calcination in step (4) is from 0.5 to 5 hours (e.g., from 0.5 to 1.5 hours, e.g., 1 hour).
In some aspects, the present disclosure provides an ammonia slip catalyst comprising the catalytic composition of any one of the above.
In some embodiments, the ammonia slip catalyst further comprises a binder.
In some embodiments, the NH 3 conversion of the ammonia slip catalyst is 70% -100% (e.g., 70-100%, 80-100%, 90-100%, e.g., 95-100%).
In some embodiments, the ammonia slip catalyst has an N 2 selectivity of 50-100% (e.g., 60-100%, 70-100%, 80-100%, 90-100%, e.g., 95-100%).
In some aspects, the present disclosure provides a catalyst layer comprising
A first layer comprising a selective catalytic reduction catalyst;
A second layer containing the ammonia slip catalyst;
Wherein the second layer is located deeper in the catalyst layer than the first layer.
In some embodiments, in the first layer, the weight of the selective catalytic reduction catalyst > the weight of the ammonia slip catalyst is greater than or equal to 0;
in some embodiments, the weight of the ammonia slip catalyst > the weight of the selective catalytic reduction catalyst in the second layer is greater than or equal to 0.
In some embodiments, the Selective Catalytic Reduction (SCR) catalyst is a catalyst that catalyzes a Selective Catalytic Reduction (SCR) process.
In an exemplary SCR process, NH 3 selectively reacts with NO x in the presence of oxygen, and the resulting N 2 and H 2O.NOx reduction processes may involve one or more of the following chemical reactions:
1) 4NH 3+4NO+O2＝4N2+6H2 O (Standard SCR reaction)
2) 4NH 3+2NO+2NO2＝4N2+6H2 O (Rapid SCR reaction)
3) 4NH 3+3NO2＝3.5N2+6H2 O (slow SCR reaction)
In some embodiments, the selective catalytic reduction catalyst is a transition metal supported molecular sieve, such as a transition metal supported zeolite molecular sieve, such as a transition metal supported small pore zeolite molecular sieve. Transition metals include, for example, copper, iron, manganese, and cerium.
In some aspects, the present disclosure provides a catalytic device comprising a substrate and the ammonia slip catalyst described above, the ammonia slip catalyst coating at least a portion of a surface of the substrate.
In some embodiments, the substrate has a porous structure.
In some embodiments, the catalytic device comprises a catalyst layer as described above, which catalyst layer covers at least a portion of the surface of the substrate.
In some aspects, the present disclosure provides a gas treatment system comprising:
a first catalytic zone containing a selective catalytic reduction catalyst;
A second catalytic zone containing an ammonia slip catalyst;
Wherein the first catalytic zone is located upstream of the second catalytic zone relative to the gas stream to be treated passing through the system;
in some embodiments, in the first catalytic zone, the weight of the selective catalytic reduction catalyst > the weight of the ammonia slip catalyst is greater than or equal to 0;
In some embodiments, the weight of the ammonia slip catalyst > the weight of the selective catalytic reduction catalyst in the second catalytic zone is greater than or equal to 0.
In some embodiments, the first catalytic zone and the second catalytic zone are each a porous ceramic support loaded with a catalyst.
In some embodiments, the catalytic composition is deposited on a honeycomb ceramic support having a pore density of 400cpsi (pores per square inch) and a wall thickness of 6 mils, a diameter of 1 inch, a length of 3 inches, at a loading of 0.5 to 5g/inch 3 (e.g., 0.5～1g/inch3、1～2g/inch3、2～3g/inch3、3～4g/inch3、4～5g/inch3、2～2.6g/inch3 or 2.5g/inch 3), and is effective to provide an average NO conversion of 70% -100% (e.g., 70-100%, 80-100%, 90-100%, e.g., 95-100%) when tested at 150 ℃ -600 ℃ (e.g., 200 ℃, 550 ℃) with N 2 as an equilibrium gas at a feed stream comprising, 500ppmNO, 550ppmNH 3、10％O2、5％H2 O at a space velocity of 100,000hr -1.
In some embodiments, the catalytic composition is deposited on a honeycomb ceramic support having a pore density of 400cpsi (pores per square inch) and a wall thickness of 6 mils, a diameter of 1 inch, a length of 2 inches, at a loading of 0.5 to 5g/inch 3 (e.g., 0.5～1g/inch3、1～2g/inch3、2～3g/inch3、3～4g/inch3、4～5g/inch3、2～2.6g/inch3 or 2.5g/inch 3), and is effective to provide an ammonia slip concentration of <10ppm when tested at 350 ℃ with the feed stream comprising 500ppmNO, 550ppmNH 3、10％O2、5％H2 O at a space velocity of 100,000hr -1, and with N 2 as an equilibrium gas.
In some embodiments, the catalytic composition is hydrothermally aged in the presence of 10% H 2 O at 700 ℃ for 50 hours with a retention of NO conversion of 50-100% (e.g., 60-100%, 70-100%, 80-100%, 90-100%, e.g., 95-100%).
In some embodiments, the catalytic composition/catalyst layer/catalytic device/gas treatment system may treat gas from a combustion process, such as from an internal combustion engine (whether mobile or stationary), a gas turbine, and a coal, fuel or natural gas-fired plant or engine. The method may also be used to treat gases from industrial processes such as refining, from refinery furnaces and boilers, smelters, chemical processing industries, coke ovens, municipal waste treatment plants and incinerators, coffee roasting plants, and the like. In one embodiment, the catalytic composition/catalyst layer/catalytic device/gas treatment system of the present invention is used to treat exhaust gas from a vehicular internal combustion engine under rich conditions, such as a gasoline engine, or a stationary engine powered by liquid petroleum gas or natural gas.
Description of the terminology:
as used herein, the term "catalyst" refers to a material that promotes the reaction.
The term "catalytic composition" refers to a combination of two or more catalysts, e.g., a combination of two different materials that promote the reaction. The catalytic composition may be in the form of a washcoat.
The term nitrogen oxides NOx denotes nitrogen oxides, in particular nitrous oxide (N 2 O), nitric Oxide (NO), nitrous oxide (N 2O3), nitrogen dioxide (NO 2), nitrous oxide (N 2O4), nitrous oxide (N 2O5), nitrogen peroxide (NO 3).
"Comprising," "including," "containing," and "containing" can mean that the content is greater than zero, such as greater than 1%, such as greater than 10%, such as greater than 20%, such as greater than 30%, such as greater than 40%, such as greater than 50%, such as greater than 60%, such as greater than 70%, such as greater than 80%, such as greater than 90%, such as greater than 100%. When the content is 100%, the meaning of "comprising", "including" and "containing" corresponds to "consisting of …".
An ammonia oxidation Catalyst (Ammonia Oxidation Catalyst, AMOX Catalyst), an Ammonia Slip Catalyst (ASC) have the same meaning in the present invention
Advantageous effects
One or more technical solutions of the present disclosure have one or more of the following beneficial effects:
(1) The catalytic composition has improved catalytic activity for ammoxidation;
(2) The catalytic composition has improved N 2 selectivity;
(3) The catalytic composition has improved resistance to hydrothermal aging;
(4) The catalytic composition has simple preparation method, low cost and suitability for large-scale application.
Drawings
FIG. 1 shows a schematic catalyst layout of a catalytic device;
fig. 2 shows a schematic catalyst layout of a further catalyst layer.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The drugs or instruments used were conventional products available commercially without the manufacturer's attention.
Example 1.1 [ WMnCeZrO x powder ]
Preparation of composite oxide (WMnCeZrO x) powder:
Ammonium metatungstate (NH 4)6H2W12O40, manganese acetate Mn (CH 3COO)2, cerium nitrate Ce (NO 3)3, zirconyl nitrate ZrO (NO 3)2: W: mn: ce: zr=1:1:1) is mixed and dissolved in deionized water according to the molar ratio, uniformly stirred, heated to 70 ℃, then 20% ammonia water is slowly added dropwise to generate precipitate until the pH value is regulated to be 8, stirring is kept at 70 ℃ for 20min, suction filtration is carried out, the obtained filter cake is dried at 120 ℃ for 2h, then baked for 1h with 850 ℃, and finally the baked solid is ground into powder.
The above composite oxide powder is subsequently used as an ammonia slip catalyst powder.
Example 1.2 [ WMnCeZrO x slurry ]
Preparation of composite oxide (WMnCeZrO x) slurry:
The WMnCeZrO x powder prepared in example 1.1 was added to deionized water, and a certain amount of surfactant was added, the slurry particle size was ground to D90 of 6-9 μm, the slurry was adjusted to ph=8-9 with ammonia water, and finally the slurry concentration was adjusted to 40wt% solids content.
The above composite oxide slurry is used as an ammonia slip catalyst slurry (ASC catalyst slurry) in the subsequent examples.
Example 2.1 [ WMnCeZrO x catalytic unit ]
Preparation of an ammonia slip catalytic device:
A 400cpsi (cells per square inch) cell density and 6 mil wall thickness, 1 inch diameter by 3 inch long honeycomb ceramic support was provided. The composite oxide slurry prepared in example 1.2 was coated on a honeycomb ceramic support. The coated support was dried at 120℃for 1 hour and calcined at 450℃for 30 minutes to obtain the catalytic device of the present example. The total catalyst coating dry weight was 2.5g/inch 3.
Example 2.2 [ SCR+ WMnCeZrO x layered catalytic device ]
Fig. 1 shows a schematic catalyst layout of a catalytic device, as shown in the figure, wherein the catalytic device comprises an upstream zone 11 and a downstream zone 12 with respect to the flow direction of the gas stream 6 to be treated passing through the catalytic device. The upstream zone 11 contains SCR catalyst and the downstream zone 12 contains ASC catalyst.
The preparation method of the catalytic device comprises the following steps:
a 400cpsi (cells per square inch) cell density and 6 mil wall thickness, 1 inch diameter by 3 inch long honeycomb ceramic support was provided.
A selective catalytic reduction catalyst slurry (SCR catalyst slurry) is provided, which is prepared by the following method: a certain amount of copper acetate and molecular sieve are added into deionized water and stirred for 30 minutes, dilute acetic acid and zirconium acetate binder (containing 30% zro 2) are added into the slurry with stirring, a certain amount of surfactant is added to adjust the slurry property, grinding is carried out, finally the slurry concentration is adjusted to 40% solid content, the copper load in the slurry is 4wt%, and the copper load is the weight percentage of "CuO/(cuo+molecular sieve)".
Along the length direction of the honeycomb ceramic carrier, the honeycomb ceramic carrier is divided into an upstream coating area and a downstream coating area, and the length ratio of the upstream coating area to the downstream coating area is 2:1. The SCR catalyst slurry was coated on the upstream region of the support, the ASC catalyst slurry prepared in example 1.2 above was coated on the downstream region of the support, the coated support was dried at 120 ℃ for 1h, and calcined at 450 ℃ for 30 minutes to obtain the catalytic device of example 2.1. The total catalyst coating dry weight was 2.5g/inch 3 and the coating dry weight ratio of the upstream zone and downstream zone was 2:1.
Example 2.3 [ SCR+ WMnCeZrO x layered catalytic device ]
Fig. 2 shows a schematic catalyst layout of a further catalytic device, which catalytic device comprises a catalyst layer 2, as shown, the catalyst layer 2 comprising a first layer 21, the first layer 21 containing a first layer molecular sieve containing copper elements with a loading of 4.5%; a second layer 22, the second layer 22 comprising a second molecular sieve, the second molecular sieve comprising copper element at a loading of 4.8%. The second layer is located deeper in the catalyst layer than the first layer, i.e. the second layer 22 is further from the gas stream 6 to be treated than the first layer 21.
A honeycomb ceramic support having a cell density of 400cpsi (cells per square inch) and a wall thickness of 6 mils, a diameter of 1 inch, and a length of 2 inches was provided.
The ASC catalyst slurry prepared in example 1.2 was coated on the above support, and dried at 120 ℃ for 1 hour after the coating as a lower coating. The SCR catalyst slurry (same as example 2.2) was then applied to the washcoat, and dried at 120 ℃ for 1 hour after application as an upper coating. The coated support was calcined at 450 ℃ for 30 minutes to obtain the catalytic device of this example 2.2. The total coating dry weight of the catalytic device was 2.5g/inch 3, and the coating dry weight ratio of the upper coating to the lower coating was 4:1.
Comparative example 1.1 [ MnCeZrO x catalytic unit ] comparative example 1.1 differs from example 2.1 in the composition of the ASC catalyst slurry. In this comparative example, the ASC catalyst slurry was prepared as follows:
(1) Preparation of composite oxide (MnCeZrO x) powder: manganese acetate Mn (CH 3COO)2, cerium nitrate Ce (NO 3)3, zirconium oxynitrate ZrO (NO 3)2) are mixed and dissolved in deionized water according to the molar ratio of W: mn: ce: zr=1:1:1, the mixture is uniformly stirred, heated to 70 ℃, then 20% ammonia water is slowly added dropwise to generate precipitate until the pH value is regulated to be 8, stirring is kept at 70 ℃ for 20min, suction filtration is carried out, the obtained filter cake is dried at 120 ℃ for 2h, then the filter cake is roasted with 850 ℃ for 1h, and finally the roasted solid is ground into powder.
(2) The MnCeZrO x powder prepared above was added to deionized water, and a certain amount of surfactant was added, the slurry particle size was ground to D90 of 6-9 μm, the slurry was adjusted to ph=8-9 with aqueous ammonia, and finally the slurry concentration was adjusted to 40wt% solids content.
The procedure parameters were identical to those of example 2.1, except for the above differences, to obtain the catalytic device of this comparative example.
Comparative example 1.2 [ SCR+ MnCeZrO x zone catalytic device ]
Comparative example 1.2 differs from example 2.2 in the composition of the ASC catalyst slurry.
The preparation method of the ASC catalyst slurry of this example is as follows:
(1) Preparation of composite oxide (MnCeZrO x) powder: manganese acetate Mn (CH 3COO)2, cerium nitrate Ce (NO 3)3, zirconium oxynitrate ZrO (NO 3)2) are mixed and dissolved in deionized water according to the molar ratio of W: mn: ce: zr=1:1:1, the mixture is uniformly stirred, heated to 70 ℃, then 20% ammonia water is slowly added dropwise to generate precipitate until the pH value is regulated to be 8, stirring is kept at 70 ℃ for 20min, suction filtration is carried out, the obtained filter cake is dried at 120 ℃ for 2h, then the filter cake is roasted with 850 ℃ for 1h, and finally the roasted solid is ground into powder.
(2) The MnCeZrO x powder prepared above was added to deionized water, and a certain amount of surfactant was added, the slurry particle size was ground to D90 of 6-9 μm, the slurry was adjusted to ph=8-9 with aqueous ammonia, and finally the slurry concentration was adjusted to 40wt% solids content.
The procedure parameters were identical to those of example 2.2, except for the above differences, to obtain the catalytic device of this comparative example.
Comparative example 1.3 [ scr+ MnCeZrO x layered catalytic unit ]
Comparative example 1.3 differs from example 2.3 in the composition of the ASC catalyst slurry.
The preparation method of the ASC catalyst slurry of this example is as follows:
(1) Preparation of composite oxide (MnCeZrO x) powder: manganese acetate Mn (CH 3COO)2, cerium nitrate Ce (NO 3)3, zirconium oxynitrate ZrO (NO 3)2) are mixed and dissolved in deionized water according to the molar ratio of W: mn: ce: zr=1:1:1, the mixture is uniformly stirred, heated to 70 ℃, then 20% ammonia water is slowly added dropwise to generate precipitate until the pH value is regulated to be 8, stirring is kept at 70 ℃ for 20min, suction filtration is carried out, the obtained filter cake is dried at 120 ℃ for 2h, then the filter cake is roasted with 850 ℃ for 1h, and finally the roasted solid is ground into powder.
(2) The MnCeZrO x powder prepared above was added to deionized water, and a certain amount of surfactant was added, the slurry particle size was ground to D90 of 6-9 μm, the slurry was adjusted to ph=8-9 with aqueous ammonia, and finally the slurry concentration was adjusted to 40wt% solids content.
The procedure parameters were identical to those of example 2.3, except for the above differences, to obtain the catalytic device of this comparative example.
Comparative example 2.1 [ SCR+Pt layered catalytic device ]
The difference from example 2.1 is the composition of the ASC catalyst slurry. In this comparative example, the ASC catalyst slurry was prepared as follows:
A certain amount of platinum nitrate solution is immersed on 5% SiO 2/Al2O3 powder in an equal volume, the immersed noble metal powder is added into deionized water for stirring, a certain amount of surfactant is added to adjust the slurry property, grinding is carried out, and finally the slurry concentration is adjusted to 40% solid content.
The procedure parameters were identical to those of example 2.2, except for the above differences, to obtain the catalytic device of this comparative example. The dry coating weight of the honeycomb porous catalytic device was 2.5g/inch 3 and the platinum (Pt) loading was 2g/ft 3.
Analytical test 1: catalytic reaction test
Providing a reactor containing the catalysts of the above examples and comparative examples, introducing a gas to be catalyzed into the reactor, wherein the gas comprises the following components: 500ppmNO, 550ppmNH 3、10％O2、5％H2 O, and N 2 as balance gas. Catalytic oxidation treatment is carried out at a temperature ranging from 150 ℃ to 600 ℃ and a space velocity of 100,000h -1. The amounts of ammonia, NO 2 and N 2 O in the gas before and after catalysis were analyzed with a Fourier Transform Infrared (FTIR) detector. The NO conversion and the slip (ppm) of NH 3 were calculated by the following formula:
wherein (1) represents the mass content of each corresponding component in the gas before the catalytic oxidation treatment and (2) represents the mass content of each corresponding component in the gas after the catalytic oxidation treatment.
Analytical test 2: hydrothermal stability test:
The freshly prepared catalytic device was subjected to a hydrothermal aging treatment. The hydrothermal aging treatment conditions were as follows: the mixture was left to stand at 700℃for 50 hours in an atmosphere having a H 2 O content of 10%. And then, carrying out a catalytic reaction test on the catalytic device subjected to the hydrothermal aging treatment, and testing the NO conversion rate and the N 2 selectivity of the catalytic device.
The low and high temperature NOx conversion and ammonia slip tests were performed with example 2.3 and comparative example 2.1, and the test results are shown in the following table.
The results in the table show that the NOx conversion and NH 3 slip for the noble metal-free examples can be approximated or equivalent to the noble metal-containing comparative examples, while the use of non-metals instead of conventional noble metal catalysts, such as platinum metal catalysts, can significantly reduce the cost of catalyst preparation, showing the potential for non-noble metal formulations.
Although specific embodiments of the invention have been described in detail, those skilled in the art will appreciate that: many modifications and variations of details may be made to the disclosed embodiments in light of the overall teachings of the invention and remain within its scope. The full scope of the invention is given by the appended claims and any equivalents thereof.
Claims (17)
1. A catalyst layer consisting of a first layer and a second layer: the first layer contains a selective catalytic reduction catalyst; the second layer contains an ammonia slip catalyst;
wherein the second layer is located deeper in the catalyst layer than the first layer;
In the first layer, the weight of the selective catalytic reduction catalyst is more than that of the ammonia slip catalyst and is more than or equal to 0;
In the second layer, the weight of the ammonia slip catalyst > the weight of the selective catalytic reduction catalyst >0;
the ammonia slip catalyst contains a catalytic composition comprising tungsten oxide, zirconium oxide, manganese oxide and cerium oxide in the following proportions, calculated on the moles of the metal elements contained in each of them: tungsten element: zirconium element: manganese element: cerium element=0.8-1.2:0.8-1.2;
and, the catalytic composition is free of platinum group metal elements;
the selective catalytic reduction catalyst is a transition metal supported molecular sieve, the transition metals including copper, iron, manganese, and cerium.
2. The catalyst layer of claim 1, having one or more of the following features:
in the presence of the catalyst composition in the presence of the catalyst,
-The tungsten oxide is WO 3;
-the zirconium oxide is ZrO 2;
-the manganese oxide comprises one or more of MnO, mnO 2、MnO3、Mn2O3、Mn2O5、Mn2O7 and Mn 3O4;
-the cerium oxide comprises CeO 2、Ce2O3.
3. The catalyst layer according to claim 1, characterized in that:
The ammonia slip catalyst is used to catalyze the following reactions:
4 NH3 + 3 O2 = 2 N2 + 6 H2O 。
4. a catalyst layer according to any one of claims 1 to 3, wherein the preparation method of the catalytic composition comprises:
(1) Providing a salt solution containing metal ions in a corresponding proportion according to the molar proportion of each metal element in the catalytic composition;
(2) Adding alkali into the solution in the previous step to precipitate metal ions;
(3) Carrying out solid-liquid separation on the product of the last step, and collecting solids;
(4) Roasting the solid in the previous step;
(5) Pulverizing the product of the last step.
5. The catalyst layer according to claim 4, characterized in that;
-in step (2) the base comprises aqueous ammonia at a concentration of 10% -30% by weight;
-heating the solution to 60-80 ℃ before adding the base in step (2);
-step (2) adding a base to the pH of the solution to 7.5-9;
-step (3) further comprises a step of drying the collected solid at 100-150 ℃;
-the calcination in step (4) is carried out at 700 ℃ -1000 ℃;
the roasting time in the step (4) is 0.5-5 hours.
6. The catalyst layer according to claim 1, characterized in that:
The NH 3 conversion rate of the ammonia slip catalyst is 70-100%.
7. The catalyst layer according to claim 1, characterized in that:
The N 2 selectivity of the ammonia slip catalyst is 50% -100%.
8. The catalyst layer according to claim 6, characterized in that: the NH 3 conversion rate of the ammonia slip catalyst is 80% -100%.
9. The catalyst layer according to claim 6, characterized in that: the NH 3 conversion rate of the ammonia slip catalyst is 90% -100%.
10. The catalyst layer according to claim 6, characterized in that: the NH 3 conversion rate of the ammonia slip catalyst is 95% -100%.
11. The catalyst layer according to claim 7, characterized in that: the N 2 selectivity of the ammonia slip catalyst is 60% -100%.
12. The catalyst layer according to claim 7, characterized in that: the N 2 selectivity of the ammonia slip catalyst is 70% -100%.
13. The catalyst layer according to claim 7, characterized in that: the N 2 selectivity of the ammonia slip catalyst is 80% -100%.
14. The catalyst layer according to claim 7, characterized in that: the N 2 selectivity of the ammonia slip catalyst is 90% -100%.
15. The catalyst layer according to claim 7, characterized in that: the N 2 selectivity of the ammonia slip catalyst is 95% -100%.
16. A catalytic device comprising a substrate and the catalyst layer of claim 1, the catalyst layer overlying at least a portion of a surface of the substrate;
The substrate has a porous structure.
17. A gas treatment system, comprising:
A first catalytic zone containing a selective catalytic reduction catalyst included in the catalyst layer of claim 1;
A second catalytic zone containing an ammonia slip catalyst included in the catalyst layer of claim 1;
Wherein the first catalytic zone is located upstream of the second catalytic zone relative to the gas stream to be treated passing through the system;
In the first catalytic zone, the weight of the selective catalytic reduction catalyst is more than that of the ammonia slip catalyst and is more than or equal to 0;
in the second catalytic zone, the weight of the ammonia slip catalyst > the weight of the selective catalytic reduction catalyst >0.
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