CN114733556A - Functionalized solid acid catalytic material, preparation method and application thereof - Google Patents
Functionalized solid acid catalytic material, preparation method and application thereof Download PDFInfo
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- CN114733556A CN114733556A CN202210408405.3A CN202210408405A CN114733556A CN 114733556 A CN114733556 A CN 114733556A CN 202210408405 A CN202210408405 A CN 202210408405A CN 114733556 A CN114733556 A CN 114733556A
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- molecular sieve
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- 239000000463 material Substances 0.000 title claims abstract description 100
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 73
- 239000011973 solid acid Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 50
- 239000002808 molecular sieve Substances 0.000 claims abstract description 49
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 39
- 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 39
- 239000010457 zeolite Substances 0.000 claims abstract description 39
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 23
- 150000003624 transition metals Chemical class 0.000 claims abstract description 23
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 17
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 10
- 231100000719 pollutant Toxicity 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 238000006722 reduction reaction Methods 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 238000003860 storage Methods 0.000 claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- 239000004332 silver Substances 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 32
- 239000002002 slurry Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000001704 evaporation Methods 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 150000002736 metal compounds Chemical class 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 150000003623 transition metal compounds Chemical class 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- -1 diesel Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 150000002500 ions Chemical class 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
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 235000012054 meals Nutrition 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 15
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000003058 platinum compounds Chemical class 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- 150000001785 cerium compounds Chemical class 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002506 iron compounds Chemical class 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- B01J29/146—Y-type faujasite
-
- 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
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
-
- 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
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
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- B01J35/393—
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/902—Multilayered catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/903—Multi-zoned catalysts
-
- 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
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- 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
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- 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
Abstract
The invention discloses a functionalized solid acid catalytic material, a preparation method and application thereof, wherein the catalytic material comprises the following components: the catalyst comprises one or more active noble metals of platinum, palladium, ruthenium and silver, transition metal serving as an auxiliary metal and a zeolite molecular sieve, wherein the active noble metal accounts for 0.01-1.0 percent of the mass percentage of a metal simple substance and exists in the form of a sub-nanocluster or a nanoparticle, and the transition metal accounts for 0.2-10 percent of the mass percentage of the metal oxide with the highest chemical valence state and exists in the form of a metal oxide with multiple chemical valence states. The invention has multiple functions of low-temperature nitrogen oxide adsorption, low-temperature gaseous organic compound adsorption, dynamic ammonia storage, ammonia selective catalytic oxidation, nitrogen oxide selective catalytic reduction and the like, can be combined with a three-way catalytic material, a selective reduction catalytic material or a nitrogen oxide storage reduction material to form a novel automobile exhaust purification system, and realizes the efficient synergistic purification of hydrocarbons, nitrogen oxides and ammonia pollutants.
Description
Technical Field
The invention relates to the technical field of catalysts, relates to a novel functional catalytic material for automobile exhaust treatment application and a preparation method thereof, and particularly relates to a functionalized solid acid catalytic material, a preparation method and application thereof.
Background
At present, more than 80% of hydrocarbon emissions of vehicles meeting the five or six emission standards in China are concentrated in the cold start stage, which usually needs to greatly increase the amount of noble metals or adopt an electric heating technology to shorten the activation time of a catalyst, so as to further improve the hydrocarbon purification capacity. However, this not only puts a great cost pressure on the automobile exhaust aftertreatment system, but also results in more complex system control.
In order to more effectively control the emission of nitrogen oxides (NOx), CN109603823A discloses a lean-burn NOx trapping catalyst, which further improves the purification capacity of NOx by utilizing the storage effect of platinum and alkaline earth metal components on NOx, however, fuel oil needs to be injected to actively regenerate the stored NOx, or wait for the accelerated driving condition to discharge excessive carbon monoxide to passively regenerate the stored NOx, and a large amount of byproducts such as ammonia and nitrous oxide are generated during the regeneration process, and at the same time, the risk of over-standard emission of hydrocarbons and carbon monoxide is increased.
The national six-emission regulation increases the requirement of the ammonia emission limit value to 10ppm, provides higher requirements for balancing fuel economy and pollutant emission reduction, and controls the emission of secondary pollutants of automobile ammonia are one of the difficulties of tail gas purification technology.
Therefore, the search for a novel multifunctional catalyst material capable of meeting the requirement of ultralow emission of multiple pollutants of the motor vehicle is a problem to be solved at present and even in future.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a functionalized solid acid catalytic material with multiple functions of low-temperature nitrogen oxide adsorption, low-temperature gaseous organic compound adsorption, dynamic ammonia storage, ammonia selective catalytic oxidation, nitrogen oxide selective catalytic reduction and the like, wherein the solid acid catalytic material can be combined with a three-way catalytic (TWC) material in any mode and can also be combined with a Selective Catalytic Reduction (SCR) or NOx Storage Reduction (NSR) catalytic material in a limited mode, so that a multifunctional catalyst or a multifunctional catalyst system is obtained, and the emission control requirements of hydrocarbon, nitrogen oxide or ammonia pollutants of gasoline vehicles, diesel vehicles, gas vehicles and hybrid vehicles are met.
According to a first aspect, the functionalized solid acid catalytic material of the present invention comprises an active noble metal, a promoter metal, and a zeolitic molecular sieve.
The active noble metal is one or more of platinum, palladium, ruthenium and silver, and the mass percentage content of the active noble metal calculated by the metal simple substance is 0.01-1.0%; the active noble metal exists in the form of sub-nanocluster or nanoparticle, and the particle size of the active noble metal is 0.2-80 nm.
The auxiliary metal is one or more transition metals of vanadium, chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, cerium, praseodymium, tungsten and rhenium, and the mass percentage content of the auxiliary metal calculated by the metal oxide with the highest chemical valence state is 0.2-10%; the promoter metals are present in the form of metal oxides, and each metal has two or more chemical valence states coexisting to stabilize active noble metal species, provide surface oxygen species activation sites, and selectively catalyze NOx reduction active sites; the particle size of the metal oxide is 0.5 nm-50 nm.
Further, the zeolite molecular sieve is one or more of Beta, Y, USY, 13X, MCM-41, MCM-68, MOR, ZSM-5, ZSM-12, ZSM-22, SSZ-13, SSZ-33 and SSZ-42, the mass percentage of the zeolite molecular sieve is 88.5% -99.79%, and SiO is SiO2With Al2O3The mass ratio of (A) to (B) is 1.5 to 50.
According to a second aspect, the method for preparing the functionalized solid acid catalytic material specifically comprises the following steps:
(1) preparation of aqueous Metal Compound solutions
Uniformly dispersing a single water-soluble noble metal compound in deionized water to prepare a noble metal compound aqueous solution, wherein the concentration of noble metal ions is 0.02 mmol/L-100 mmol/L.
Uniformly dispersing a single water-soluble transition metal compound in deionized water to prepare a transition metal compound aqueous solution, wherein the concentration of transition metal ions is 1 mmol/L-800 mmol/L.
When two or more noble metals or transition metal compounds are involved, aqueous solutions are prepared separately for later use.
(2) Preparation of zeolite molecular sieve slurry
Uniformly dispersing the zeolite molecular sieve in deionized water to prepare a zeolite molecular sieve blank slurry, wherein the solid content of the slurry is 20-45%.
Or the noble metal loaded zeolite molecular sieve is uniformly dispersed in deionized water to prepare noble metal loaded noble metal zeolite molecular sieve slurry, and the solid content of the slurry is 20-45%.
Or uniformly dispersing the transition metal loaded zeolite molecular sieve in deionized water to prepare transition metal loaded zeolite molecular sieve slurry, wherein the solid content of the slurry is 20-45%.
(3) Dispersion of noble and transition metal components
Dropwise adding the aqueous solution of the noble metal obtained in the step (1) into the blank slurry of the zeolite molecular sieve obtained in the step (2), continuously stirring for 0.5-6 h, and evaporating at 50-100 ℃ until the solid content is more than 65%.
Or dropwise adding the transition metal aqueous solution obtained in the step (1) into the zeolite molecular sieve blank slurry obtained in the step (2), continuously stirring for 0.5-6 h, and evaporating at 50-100 ℃ until the solid content is more than 65%.
Dropwise adding the noble metal aqueous solution obtained in the step (1) into the transition metal loaded zeolite molecular sieve slurry obtained in the step (2), continuously stirring for 0.5-6 h, and evaporating at 50-100 ℃ until the solid content is more than 65%.
Or dropwise adding the transition metal aqueous solution obtained in the step (1) into the noble metal loaded zeolite molecular sieve slurry obtained in the step (2), continuously stirring for 0.5-6 h, and evaporating at 50-100 ℃ until the solid content is more than 65%.
Or dropwise adding the noble metal aqueous solution obtained in the step (1) into the zeolite molecular sieve blank slurry obtained in the step (2), continuously stirring for 0.5-6 h, continuously dropwise adding the transition metal aqueous solution, continuously stirring for 5-60 min, and evaporating at 50-100 ℃ until the solid content is over 65%.
(4) Thermal treatment of catalytic materials
The evaporation treatment process is accompanied with continuous mechanical stirring or rotary evaporation mode, drying is carried out by adopting blast drying equipment, the drying temperature is 80-200 ℃, the drying time is 5-24 h, and then the obtained powder is ground to the granularity D502-50 μm. And (3) roasting the catalytic material at high temperature of 350-780 ℃ for 0.2-10 h by adopting a muffle furnace or a calciner.
According to a third aspect, the use of the functionalized solid acid catalytic material of the present invention comprises:
(1) the catalyst can be combined with a three-way catalyst (TWC) material in any mode, and can also be combined with a Selective Catalytic Reduction (SCR) material and a nitrogen oxide storage reduction (NSR) catalytic material in a limited mode, so that a multifunctional catalyst or a multifunctional catalyst system is obtained, and the emission control requirements of hydrocarbon, nitrogen oxide or ammonia pollutants of gasoline vehicles, diesel vehicles, gas vehicles and hybrid vehicles are met.
Further, the combined application of any one of the manners means that the combination manner between the functionalized solid acid catalytic material and the TWC material is not limited by physical structure.
Further, the combined application of the limiting modes is limited to: the functionalized solid acid catalytic material is uniformly distributed on the surface of the SCR material coating, or the functionalized solid acid catalytic material is uniformly distributed at the rear end of the SCR and NSR material coating area, or a close coupling system of the SCR or NSR catalyst and the functionalized solid acid catalyst is formed.
Further, the mass percentage content of the TWC material, the SCR material or the NSR material is 15-80%, and the mass percentage content of the functionalized solid acid catalytic material is 20-85%.
Mechanism of the present invention
In order to realize the purpose of the invention, the inventor constructs a multifunctional active site by analyzing the exhaust characteristics of the automobile under all working conditions, utilizing the dynamic adsorption effect of the solid acid catalytic material on nitrogen oxides, hydrocarbons and ammonia and carrying out functional treatment on the surface of the material so as to improve the adsorption strength of nitrogen oxides and hydrocarbon molecules and the reduction activity of nitrogen oxides; providing surface oxygen species activation sites to promote low temperature oxidation of adsorbed hydrocarbon molecules; the variable valence characteristics of the metal promoter oxide ensure that the active species can be maintained in the inherent state for a long time, and the service life of the catalyst is prolonged, such as:
(1) when the TWC ignition temperature is approached or reached, nitrogen oxides and hydrocarbon molecules captured in cold start are released and then are catalytically converted into nitrogen, carbon dioxide and water on the surface of noble metal particles of a solid acid catalytic material or a three-way catalytic material;
(2) NH generated by preposed TWC or NSR system3The byproduct molecules and the nitrogen oxide molecules captured in cold start generate nitrogen and water under the catalytic action of the solid acid material;
(3) NH leaked by front SCR system3The molecules are oxidized into nitrogen and water with high selectivity under the catalysis of the solid acid material;
(4) nitrogen oxide molecules which cannot be purified by a TWC system during deceleration and fuel cut of a vehicle and NH stored by a solid acid catalytic material3Generating nitrogen and water by SCR reaction;
(5) NH generated during regeneration of a pre-NSR system3The molecules and the nitrogen oxide molecules generate nitrogen and water under the working condition of excessive oxygen under the catalytic action of the solid acid material.
The invention has the advantages of
Experiments show that compared with the existing post-treatment catalyst technology of gasoline vehicles, gas vehicles or diesel vehicles, the invention has the beneficial effects that:
(1) the invention has higher nitrogen yield and shows excellent NH3The oxidation reaction performance is favorable for the clean emission of nitrogen-containing automobile exhaust;
(2) the invention has the low-temperature trapping effect on cold start hydrocarbon and nitrogen oxide molecules and NH generated by the catalytic effect of the preposed TWC3The by-product has the selective catalytic reduction effect on nitrogen oxide discharged under the speed reduction and oil cut-off working conditions;
(3) the invention can realize the cooperative purification of nitrogen oxide, hydrocarbon and ammonia pollutants, has higher applicability to transient working conditions, is not only suitable for the traditional gasoline vehicle, diesel vehicle and gas vehicle pollutant ultra-low emission post-treatment system, but also suitable for the hybrid vehicle post-treatment system with frequent start-stop characteristics. The invention effectively controls NH while solving the technical bottleneck problem of ultralow emission control of hydrocarbon and nitrogen oxide3And the emission of byproducts, thereby meeting the six national emission standards and even higher emission standards.
Drawings
FIG. 1 TEM image of a powder of the functionalized solid acid catalytic material of the present invention.
FIG. 2 Fe of example 1 of the present invention2O3TEM images of Pt/USY catalytic materials.
Detailed Description
According to the scope defined by the invention, the addition amount of the noble metal compound, the transition metal compound and the zeolite molecular sieve (or the noble metal-loaded zeolite molecular sieve or the transition metal-loaded zeolite molecular sieve) is calculated and determined according to the chemical composition and the total mass of the catalytic material to be prepared, and is weighed for standby.
Calculating deionized water according to the addition amounts of the noble metal compound and the transition metal compound and the concentration of the solution to be prepared, weighing and placing in a beaker or a stirring kettle, starting a stirrer for continuous stirring, adding the noble metal compound or the transition metal compound, and continuously stirring to fully dissolve the noble metal compound or the transition metal compound to respectively obtain a noble metal compound aqueous solution and a transition metal compound aqueous solution.
Weighing deionized water according to the solid content of the predetermined slurry of 20-45%, placing the deionized water in a beaker or a stirring kettle, starting a stirrer to continuously stir, adding, starting the stirrer to continuously stir, adding the zeolite molecular sieve, the noble metal loaded zeolite molecular sieve or the transition metal loaded zeolite molecular sieve, and continuously stirring to obtain uniform and continuous molecular sieve slurry.
Adding a noble metal compound aqueous solution or a transition metal compound aqueous solution, continuously stirring for 0.5 to 6 hours, particularly, adding the noble metal compound aqueous solution, stirring for 0.5 to 6 hours, adding the transition metal aqueous solution, stirring for 5 to 60 minutes, performing evaporation treatment at 50 to 100 ℃ until the solid content is more than 65 percent, and drying, grinding and roasting to obtain the functionalized solid acid catalytic material powder (shown in figure 1).
Preparing a multifunctional catalyst or constructing a multifunctional catalyst system according to the limited mode of the material combination application. In particular, the manner of combination between the functionalized solid acid catalytic material and the TWC material is not limited by physical structure; the functionalized solid acid catalytic material is uniformly distributed on the surface of the SCR material coating, or the functionalized solid acid catalytic material is uniformly distributed at the rear end of the SCR and NSR material coating area, or a close coupling system of the SCR or NSR catalyst and the functionalized solid acid catalyst is formed.
In order to make the technical means and the creative features of the invention clearer and easier to understand, the invention is further explained with the embodiment.
Example 1
0.842 g of a water-soluble platinum compound of platinum was weighed and dissolved sufficiently in 85mL of deionized water to obtain an aqueous solution of the platinum compound of about 50mmol/L for further use.
1.75 g of a water-soluble iron compound of iron was weighed and dissolved sufficiently in 60mL of deionized water to obtain an aqueous iron compound solution of about 500mmol/L for use.
99.16 g of USY molecular sieve subjected to standing at 500 ℃ and air full dehydration treatment is weighed and fully dispersed in 150mL of deionized water to obtain USY molecular sieve blank slurry with the solid content of about 40%, the prepared platinum compound aqueous solution is added, the stirring is continued for 5h, and then the evaporation treatment is carried out at 80 ℃ until the solid content is about 70%. Drying at 120 ℃ for 12h, grinding, and dehydrating at 300 ℃ to obtain platinum-loaded USY molecular sieve powder.
Weighing 47.5 g of platinum-loaded USY molecular sieve powder, fully dispersing in 149mL of deionized water, fully dispersing in 70mL of deionized water to obtain platinum-loaded USY molecular sieve slurry with the solid content of about 40%, adding the prepared iron compound aqueous solution, continuously stirring for 1h, and then evaporating at 80 ℃ until the solid content is about 70%. Drying at 120 ℃ for 12h, grinding, standing at 600 ℃ and roasting in air for 4h to obtain Fe2O3-Pt/USY catalytic material.
As shown in FIG. 2, Fe of the present invention2O3The size of the platinum nanoparticles in the-Pt/USY catalytic material is about 15nm, Fe2O3The particle size was about 10 nm.
For Fe of the present invention2O3Platinum loading and Fe for-Pt/USY catalytic materials, respectively2O3Content test, test result shows: the mass percentage of the platinum simple substance is 0.77 percent, and the Fe content2O3The mass percentage of (B) is 4.7%.
For Fe of the present invention2O3-Pt/USY catalytic material for NH3The oxidation reaction performance was measured, and the results are shown in table 1.
TABLE 1Fe2O3Comparison of Nitrogen yields of Pt/USY and Pt/USY catalytic materials
| |
200℃ | 250℃ | 300℃ | 350℃ | 400℃ |
| Pt/USY catalytic material | 92.3％ | 52.6％ | 29.8％ | 19.9％ | 15.1％ |
| Fe2O3-Pt/USY catalytic material | 97.8％ | 85.4％ | 69.6％ | 48.5％ | 44.2％ |
As can be seen from Table 1, the Fe of the present invention is compared to the Pt/USY of the prior art2O3the-Pt/USY catalytic material has higher nitrogen yield and shows excellent NH3Performance of oxidation reaction.
Example 2
2 g of a water-soluble platinum compound containing palladium was weighed and dissolved sufficiently in 25mL of deionized water to obtain an aqueous solution of the platinum compound of about 80mmol/L for further use.
12.2 g of a water-soluble cerium compound of cerium was weighed and dissolved sufficiently in 250mL of deionized water to obtain an aqueous solution of the cerium compound of about 350mmol/L for use.
Weighing 483 g of beta molecular sieve subjected to 500 ℃ standing air full dehydration treatment, fully dispersing in 900mL of deionized water to obtain beta molecular sieve blank slurry with the solid content of about 35%, adding the prepared palladium compound aqueous solution, stirring for 3h, adding the prepared cerium compound aqueous solution, continuously stirring for 10min, rapidly heating to 85 ℃ and performing evaporation treatment until the solid content is about 80%. Drying at 120 deg.C for 12h, grinding, standing at 650 deg.C, and air roasting for 2h to obtain Pd/CeO2A/beta-1 # catalytic material.
Pd/CeO of the invention2The palladium nano-particle size in the/beta-1 # catalytic material is about 5nm, and CeO2The particle size is about 8nm, the mass percentage of the palladium simple substance is 0.41 percent, and CeO2The mass percentage of the silicon dioxide is 2.9 percent and the SiO content2With Al2O3The mass ratio of (2) is 26.57.
The traditional TWC material and the Pd/CeO of the invention2The/beta catalytic material is respectively pulped and then sequentially coated on a honeycomb cordierite carrier to prepare the novel TWC catalyst, wherein the mass proportion of the TWC material coating is 40 percent, and Pd/CeO2The mass proportion of the/beta material coating is 60%, the coating and a preposed TWC catalyst form a novel TWC system A after hydrothermal aging at 850 ℃, and the system is subjected to a finished automobile emission performance test, and the result is shown in Table 2.
TABLE 2 comparison of vehicle emissions Performance test results for conventional TWC and New TWC System A
| Discharging pollutants | Total hydrocarbons | Non-methane hydrocarbons | Nitrogen oxides |
| Conventional TWC system | 32.2mg/km | 28.3mg/km | 51.0mg/km |
| Novel TWC System A | 27.6mg/km | 23.9mg/km | 10.8mg/km |
As can be seen from Table 2, the vehicle emission performance of the novel TWC system A exhibited more excellent emission control capability of total hydrocarbons, non-methane hydrocarbons, nitrogen oxides, due to Pd/CeO of the present invention, as compared to the conventional TWC system2Low temperature trapping effect of/beta catalytic material on cold start hydrocarbon and nitrogen oxide molecules and NH generated by front TWC catalysis3The by-product has the selective catalytic reduction function on nitrogen oxide discharged under the speed-reducing and oil-cutting working conditions.
Example 3
Further, Pd/CeO was prepared according to the procedure and scheme of example 22Catalyst material No./beta-2, Pd/CeO2/β-1#、Pd/CeO2The characterization analysis of the/beta-2 # catalytic material and the results of the ethylene low-temperature adsorption performance test are shown in tables 3 and 4 respectively.
TABLE 3Pd/CeO2Beta-1 # and Pd/CeO2Comparison of characterization and analysis results of/beta-2 # catalytic material
TABLE 4Pd/CeO2Beta-1 # and Pd/CeO2Comparison of ethylene low-temperature adsorption performance test results of/beta-2 # catalytic material
| Assay item | Total adsorption capacity | Effective adsorption amount | Effective adsorption efficiency |
| Pd/CeO2/β-1# | 31.23μmol/g | 20.47μmol/g | 32.42％ |
| Pd/CeO2/β-2# | 14.42μmol/g | 7.37μmol/g | 11.68％ |
As is clear from tables 3 and 4, the amount of Pd supported and CeO supported2The content is respectively increased to 1.19 percent and 12.2 percent, which is not beneficial to low-temperature adsorption of ethylene, the utilization rate of palladium atoms is only 54.3 percent of that when the load of Pd is kept to be 0.41 percent, because the excessive metal or metal oxide on the surface of the molecular sieve material is deposited to cause that a large number of original surface acid sites are covered, and the excessive molecular density of the cerium compound inhibits the impregnation adsorption of the palladium compound, thereby causing the dispersibility of palladium particles, the acid sites and the metal active sitesThe synergy is reduced.
Therefore, the addition of excessively high active noble metals and metal assistants not only reduces the utilization rate of metal atoms and increases the cost of the catalyst, but also is not beneficial to improving the performance of the material.
Claims (10)
1. A functionalized solid acid catalytic material comprises an active noble metal, an auxiliary metal and a zeolite molecular sieve; the method is characterized in that:
the active noble metal is one or more of platinum, palladium, ruthenium and silver, the mass percentage content of the active noble metal calculated by metal simple substance is 0.01-1.0%, the active noble metal exists in the form of sub-nanocluster or nanoparticle, and the particle size of the active noble metal is 0.2-80 nm;
the auxiliary metal is one or more transition metals of vanadium, chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, cerium, praseodymium, tungsten and rhenium, the mass percentage content of the auxiliary metal calculated by the metal oxide with the highest chemical valence state is 0.2-10%, the transition metal exists in the form of oxide, each metal has two or more than two chemical valence states coexisting and is used for stabilizing active noble metal species, providing surface oxygen species activation sites and selective catalytic NOx reduction active sites, and the particle size of the metal oxide is 0.5-50 nm.
2. The functionalized solid acid catalytic material of claim 1, characterized in that:
the zeolite molecular sieve is one or more of Beta, Y, USY, 13X, MCM-41, MCM-68, MOR, ZSM-5, ZSM-12, ZSM-22, SSZ-13, SSZ-33 and SSZ-42.
3. The functionalized solid acid catalytic material of claim 2, wherein:
the mass percentage content of the zeolite molecular sieve in the functionalized solid acid catalytic material is 89-99.79%;
SiO in the zeolite molecular sieve2With Al2O3The mass ratio of (A) to (B) is 1.5 to 50.
4. A method of preparing a functionalized solid acid catalytic material according to any one of claims 1 to 3, comprising the steps of:
step (1), preparation of aqueous solution of metal compound
Uniformly dispersing a single water-soluble noble metal compound in deionized water to prepare a noble metal compound aqueous solution, wherein the concentration of noble metal ions is 0.02 mmol/L-100 mmol/L;
uniformly dispersing a single water-soluble transition metal compound in deionized water to prepare a transition metal compound aqueous solution, wherein the concentration of transition metal ions is 1 mmol/L-800 mmol/L;
when two or more noble metals or transition metal compounds are involved, aqueous solutions are prepared separately for later use;
step (2), preparation of zeolite molecular sieve slurry
Uniformly dispersing the zeolite molecular sieve in deionized water to prepare a zeolite molecular sieve blank slurry, wherein the solid content of the slurry is 20-45%;
or the noble metal loaded zeolite molecular sieve is uniformly dispersed in deionized water, and noble metal loaded zeolite molecular sieve slurry is prepared, wherein the solid content of the slurry is 20-45%;
or uniformly dispersing the transition metal loaded zeolite molecular sieve in deionized water to prepare transition metal loaded zeolite molecular sieve slurry, wherein the solid content of the slurry is 20-45%;
step (3), dispersion of noble metal and transition metal components
Dropwise adding the aqueous solution of the noble metal obtained in the step (1) into the zeolite molecular sieve blank slurry obtained in the step (2), continuously stirring for 0.5-6 h, evaporating at 50-100 ℃ until the solid content is more than 65%, and drying, grinding and roasting to obtain noble metal-loaded zeolite molecular sieve powder;
or dropwise adding the transition metal aqueous solution obtained in the step (1) into the zeolite molecular sieve blank slurry obtained in the step (2), continuously stirring for 0.5-6 h, evaporating at 50-100 ℃ until the solid content is more than 65%, and drying, grinding and roasting to obtain transition metal loaded zeolite molecular sieve powder;
dropwise adding the aqueous solution of the noble metal obtained in the step (1) into the transition metal-loaded zeolite molecular sieve slurry obtained in the step (2), continuously stirring for 0.5-6 h, evaporating at 50-100 ℃ until the solid content is more than 65%, and drying, grinding and roasting to obtain functional solid acid catalytic material powder;
or dropwise adding the transition metal aqueous solution obtained in the step (1) into the noble metal-loaded zeolite molecular sieve slurry obtained in the step (2), continuously stirring for 0.5-6 h, evaporating at 50-100 ℃ until the solid content is over 65%, and drying, grinding and roasting to obtain functionalized solid acid catalytic material powder;
or dropwise adding the noble metal aqueous solution obtained in the step (1) into the zeolite molecular sieve blank slurry obtained in the step (2), continuously stirring for 0.5-6 h, continuously dropwise adding the transition metal aqueous solution, continuously stirring for 5-60 min, evaporating at 50-100 ℃ until the solid content is over 65%, and drying, grinding and roasting to obtain the functionalized solid acid catalytic material powder.
5. The method of claim 4, wherein the functionalized solid acid catalytic material comprises:
the evaporation treatment process is accompanied by continuous mechanical stirring or rotary evaporation mode.
6. The method of claim 4, wherein the functionalized solid acid catalytic material comprises:
the drying temperature is 80-200 ℃, and the drying time is 5-24 h;
the grinding process grinds the meal to a particle size D502-50 μm;
the roasting temperature is 350-780 ℃, and the roasting time is 0.2-10 h.
7. Use of a functionalized solid acid catalytic material according to any one of claims 1 to 3, wherein:
combined with a three-way catalyst (TWC) material in any way, or combined with a Selective Catalytic Reduction (SCR) material, a nitrogen oxide storage reduction (NSR) catalytic material in a defined way, for obtaining a multifunctional catalyst or a multifunctional catalyst system, meeting hydrocarbon, nitrogen oxide, or ammonia pollutant emission control requirements of gasoline, diesel, gas, hybrid vehicles.
8. Use of the functionalized solid acid catalytic material according to claim 7, characterized in that:
the combined application of any one of the manners means that the combination manner between the functionalized solid acid catalytic material and the TWC material is not limited by physical structure.
9. Use of the functionalized solid acid catalytic material according to claim 7, characterized in that:
the combined application of the limiting modes is limited to: the functionalized solid acid catalytic material is uniformly distributed on the surface of the SCR material coating, or the functionalized solid acid catalytic material is uniformly distributed at the rear end of the SCR material coating area or the NSR material coating area, or a close coupling system of the SCR or NSR catalyst and the functionalized solid acid catalyst is formed.
10. Use of a functionalized solid acid catalytic material according to any one of claims 7 to 9, characterized in that:
the mass percentage of the TWC material, the SCR material or the NSR material is 15-80%, and the mass percentage of the functionalized solid acid catalytic material is 20-85%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115532302B (en) * | 2022-10-18 | 2024-02-02 | 中国科学院大连化学物理研究所 | Ultra-thin molecular sieve nano-sheet domain-limited high-dispersion Rh atomic cluster catalyst and preparation method and application thereof |
| CN116251592A (en) * | 2023-01-31 | 2023-06-13 | 昆明贵研催化剂有限责任公司 | Post-treatment catalyst for hybrid electric vehicle, preparation method and application thereof |
| CN116251592B (en) * | 2023-01-31 | 2023-12-12 | 昆明贵研催化剂有限责任公司 | Post-treatment catalyst for hybrid electric vehicle, preparation method and application thereof |
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